Polymerizable compound, polymerizable composition, polymer, and optically anisotropic product

ABSTRACT

This invention provides a polymerizable compound represented by formula (I), a polymerizable composition containing the polymerizable compound and a polymerization initiator, a polymer produced by polymerizing the polymerizable compound or the polymerizable composition, and an optically anisotropic product comprising the polymer as a constituent material. In formula (1), Y 1  to Y 9  represent —O—, —S—, —O—C(═O)—, —C(═O)—O— or the like, G 1  and G 2  represent a divalent linear aliphatic group having 1 to 20 carbon atoms or the like, Z 1  to Z 3  represent an alkenyl group having 2 to 10 carbon atoms or the like, A x  represents a group represented by a formula (II), wherein X represents an oxygen atom, a sulfur atom or the like, 
     D represents an alkylene group having 1 to 20 carbon atoms or the like, A 1  represents a trivalent aromatic group or the like, A 2  and A 3  represent a divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms or the like, A 4  and A 5  represent a divalent aromatic group having 4 to 30 carbon atoms or the like, Q 1  represents an alkyl group having 1 to 6 carbon atoms or the like, and m and n are 0 or 1.

TECHNICAL FIELD

The present invention relates to a polymerizable compound, apolymerizable composition, and a polymer that can produce an opticalfilm that achieves uniform conversion of polarized light over a widewavelength band, and does not show a change in wavelength dispersioneven when the dose of ultraviolet rays applied to effect curing isincreased, and also relates to an optically anisotropic product.

BACKGROUND ART

A flat panel display (FPD) that utilizes an optical film (e.g.,polarizer and retardation film) can achieve high-resolution display, andhas been widely used as a display device that exhibits excellentperformance.

A quarter-wave plate that converts linearly polarized light intocircularly polarized light, a half-wave plate that changes the plane ofvibration of linearly polarized light by 900, and the like are known.Such a retardation film can achieve accurate conversion of specificmonochromatic light so that ¼λ or ½λ retardation occurs.

However, a known retardation film has a problem in that polarized lightthat passes through is converted into colored polarized light.Specifically, since a material that forms the retardation film haswavelength dispersion with respect to retardation, and a polarizationstate distribution corresponding to each wavelength occurs with respectto white light that includes different light rays in the visible region,it is impossible to achieve accurate ¼λ or ½λ retardation over theentire wavelength band.

In order to solve the above problem, various types of widebandretardation films that can achieve uniform retardation with respect tolight over a wide wavelength band (i.e., retardation films havingreverse wavelength dispersion) have been studied (see Patent Literature1 to 6, for example).

It has been desired to reduce the thickness of a flat panel display asmuch as possible along with an improvement in performance and widespreaduse of mobile information terminals (e.g., mobile personal computers andmobile phones). Therefore, a reduction in thickness of the retardationfilm has also been desired.

It has been considered that it is most effective to produce aretardation film by applying a polymerizable composition that includes alow-molecular-weight polymerizable compound to a film substrate in orderto reduce the thickness of the retardation film. Variouslow-molecular-weight polymerizable compounds having excellent wavelengthdispersion, and various polymerizable compositions using suchpolymerizable compounds have been developed (see Patent Literature 7 to24, for example).

However, the low-molecular-weight polymerizable compounds or thepolymerizable compositions disclosed in Patent Literature 7 to 24 have anumber of problems in that reverse wavelength dispersion may beinsufficient, or it may be difficult to apply the low-molecular-weightpolymerizable compounds or the polymerizable compositions to a film dueto a high melting point that is not suitable for an industrial process,or the temperature range in which liquid crystallinity is obtained maybe very narrow, or solubility in a solvent generally used for anindustrial process may be low. Moreover, since theselow-molecular-weight polymerizable compounds and the like aresynthesized by performing a plurality of steps using a synthesis methodthat utilizes an expensive reagent, the production cost increases.

A novel polymerizable hydrazone compound and a novel polymerizable azinecompound have been proposed as a liquid crystal material that may solvethese problems (see Patent Literature 25 to 30).

However, when the polymerizable azine compound is applied, dried,subjected to an alignment treatment, and photo-cured using ultravioletrays to form a polymer film, a change in wavelength dispersion may occurdepending on the dose of ultraviolet rays.

Specifically, when the polymerizable azine compound is used, reversewavelength dispersion may be lost (i.e., normal wavelength dispersionmay be obtained) when the dose of ultraviolet rays applied to effectcuring is increased.

CITATION LIST Patent Literature Patent Literature 1: JP-A-10-68816Patent Literature 2: JP-A-10-90521 Patent Literature 3: JP-A-11-52131Patent Literature 4: JP-A-2000-284126 (US20020159005A1) PatentLiterature 5: JP-A-2001-4837 Patent Literature 6: WO2000/026705 PatentLiterature 7: JP-A-2002-267838 Patent Literature 8: JP-A-2003-160540(US20030102458A1) Patent Literature 9: JP-A-2005-208414 PatentLiterature 10: JP-A-2005-208415 Patent Literature 11: JP-A-2005-208416Patent Literature 12: JP-A-2005-289980 (US20070176145A1) PatentLiterature 13: JP-A-2006-330710 (US20090072194A1) Patent Literature 14:JP-A-2009-179563 (US20090189120A1) Patent Literature 15: JP-A-2010-31223Patent Literature 16: JP-A-2011-6360 Patent Literature 17:JP-A-2011-6361 Patent Literature 18: JP-A-2011-42606 Patent Literature19: JP-T-2010-537954 (US20100201920A1) Patent Literature 20:JP-T-2010-537955 (US20100301271A1) Patent Literature 21: WO2006/052001(US20070298191A1)

Patent Literature 22: U.S. Pat. No. 6,139,771Patent Literature 23: U.S. Pat. No. 6,203,724Patent Literature 24: U.S. Pat. No. 5,567,349

Patent Literature 25: JP-A-2012-141245 Patent Literature 26:JP-A-2012-147904 Patent Literature 27: Japanese Patent Application No.2012-232315 Patent Literature 28: Japanese Patent Application No.2013-075379 Patent Literature 29: Japanese Patent Application No.2013-027240 Patent Literature 30: Japanese Patent Application No.2013-075379 SUMMARY OF INVENTION Technical Problem

The invention was conceived in view of the above situation. An object ofthe invention is to provide a polymerizable compound, a polymerizablecomposition, and a polymer that have a practical low melting point,exhibit excellent solubility in a general-purpose solvent, can beproduced at low cost, and can produce an optical film that achievesuniform conversion of polarized light over a wide wavelength band, anddoes not show a change in wavelength dispersion even when the dose ofultraviolet rays applied to effect curing is increased, and an opticallyanisotropic product.

Solution to Problem

The inventors conducted extensive studies in order to solve the aboveproblem. As a result, the inventors found that a polymerizable compoundrepresented by the following formula (I), a polymerizable compositionthat includes the polymerizable compound and an initiator, and a polymerobtained by polymerizing the polymerizable compound or the polymerizablecomposition have a practical low melting point, exhibit excellentsolubility in a general-purpose solvent, can be produced at low cost,and can produce an optically anisotropic product that achieves uniformconversion of polarized light over a wide wavelength band, and does notshow a change in wavelength dispersion even when the dose of ultravioletrays applied to effect curing is increased. This finding has led to thecompletion of the invention.

Several aspects of the invention provide the following polymerizablecompound (see (1) to (7)), polymerizable composition (see (8) and (9)),polymer (see (10) and (11)), and optically anisotropic product (see(12)).

(1) A polymerizable compound represented by the following formula (I),

wherein each of Y¹ to Y⁹ independently represents a chemical singlebond, —O—, —S—, —O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, —NR¹—C(═O)—,—C(═O)—NR¹—, —O—C(═O)—NR¹—, —NR¹—C(═O)—O—, —NR¹—C(═O)—NR¹—, —O—NR¹—, or—NR¹—O—, R¹ represents a hydrogen atom or an alkyl group having 1 to 6carbon atoms,each of G¹ and G² independently represents a substituted orunsubstituted divalent linear aliphatic group having 1 to 20 carbonatoms,each of Z¹, Z², and Z³ independently represents an alkenyl group having2 to 10 carbon atoms that is substituted with a halogen atom, orunsubstituted,A^(x) represents a group represented by the following formula (II),

wherein X represents —NR²—, an oxygen atom, a sulfur atom, —SO—, or—SO₂—, and R² represents a hydrogen atom or an alkyl group having 1 to 6carbon atoms, provided that an arbitrary C—H is optionally substitutedwith a nitrogen atom,D represents a substituted or unsubstituted alkylene group having 1 to20 carbon atoms that optionally includes —O—, —S—, —O—C(═O)—, —C(═O)—O—,—O—C(═O)—O—, —NR³—C(═O)—, —C(═O)—NR³—, —NR³—, or —C(═O)—, or asubstituted or unsubstituted cycloalkanediyl group having 3 to 20 carbonatoms, provided that a case where the alkylene group includes two ormore contiguous —O— or —S— is excluded, and R³ represents a hydrogenatom or an alkyl group having 1 to 6 carbon atoms,A¹ represents a substituted or unsubstituted trivalent aromatic group,each of A² and A³ independently represents a substituted orunsubstituted divalent alicyclic hydrocarbon group having 3 to 30 carbonatoms,each of A⁴ and A⁵ independently represents a substituted orunsubstituted divalent aromatic group having 4 to 30 carbon atoms,Q¹ represents a hydrogen atom, or a substituted or unsubstituted alkylgroup having 1 to 6 carbon atoms, and m and n are independently 0 or 1.(2) The polymerizable compound according to (1), wherein D is asubstituted or unsubstituted alkylene group having 1 to 20 carbon atomsthat optionally includes —O—, —S—, —O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, or—C(═O)—, provided that a case where the alkylene group includes two ormore contiguous —O— or —S— is excluded.(3) The polymerizable compound according to (1), wherein A¹ is asubstituted or unsubstituted trivalent benzene ring group, or asubstituted or unsubstituted trivalent naphthalene ring group.(4) The polymerizable compound according to (1), wherein each of Y¹ toY⁹ is independently a chemical single bond, —O—, —O—C(═O)—, —C(═O)—O—,or —O—C(═O)—O—.(5) The polymerizable compound according to (1), wherein each of Z¹, Z²,and Z³ is independently CH₂═CH—, CH₂═C(CH₃)—, or CH₂═C(Cl)—.(6) The polymerizable compound according to (1), wherein each of G¹ andG² is independently a substituted or unsubstituted divalent aliphaticgroup having 1 to 12 carbon atoms that optionally includes —O—,—O—C(═O)—, —C(═O)—O—, or —C(═O)—, provided that a case where thealiphatic group includes two or more contiguous —O— is excluded.(7) The polymerizable compound according to (1), wherein each of G¹ andG² is independently an alkylene group having 1 to 12 carbon atoms.(8) A polymerizable composition including at least one type of thepolymerizable compound according to any one of (1) to (7).(9) A polymerizable composition including at least one type of thepolymerizable compound according to any one of (1) to (7), and aninitiator.(10) A polymer obtained by polymerizing the polymerizable compoundaccording to any one of (1) to (7), or polymerizing the polymerizablecomposition according to (8) or (9).(11) The polymer according to (10), the polymer being a liquid crystalpolymer.(12) An optically anisotropic product including the polymer according to(11).

Advantageous Effects of Invention

The polymerizable compound, the polymerizable composition, and thepolymer according to the aspects of the invention can inexpensivelyproduce an optically anisotropic product that achieves uniformconversion of polarized light over a wide wavelength band, and does notshow a change in wavelength dispersion even when the dose of ultravioletrays applied to effect curing is increased (i.e., exhibits satisfactoryperformance).

Since the optically anisotropic product according to one aspect of theinvention is produced using the polymerizable compound, thepolymerizable composition, or the polymer according to one aspect of theinvention, the optically anisotropic product can be produced at lowcost, can achieve uniform conversion of polarized light over a widewavelength band, and exhibits satisfactory performance. In particular,the optically anisotropic product according to one aspect of theinvention does not show a change in wavelength dispersion even when thedose of ultraviolet rays applied to effect curing is changed during theproduction process. Specifically, it is possible to increase the degreeof freedom with regard to the production process.

An antireflective film may be produced by combining the film-likeoptically anisotropic product according to one aspect of the inventionwith a polarizer. The antireflective film may suitably be used as anantireflective film for a touch panel or an organic electroluminescencedevice, for example.

DESCRIPTION OF EMBODIMENTS

A polymerizable compound, a polymerizable composition, a polymer, and anoptically anisotropic product according to the exemplary embodiments ofthe invention are described in detail below.

1) Polymerizable Compound

A polymerizable compound according to one embodiment of the invention isa compound represented by the formula (I).

each of Y¹ to Y⁹ in the formula (I) independently represents a chemicalsingle bond, —O—, —S—, —O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, —NR¹—C(═O)—,—C(═O)—NR¹—, —O—C(═O)—NR¹—, —NR¹—C(═O)—O—, —NR¹—C(═O)—NR¹—, —O—NR¹—, or—NR¹—O—.

R¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbonatoms.

Examples of the alkyl group having 1 to 6 carbon atoms that may berepresented by R¹ include a methyl group, an ethyl group, an n-propylgroup, an isopropyl group, an n-butyl group, a sec-butyl group, at-butyl group, an n-pentyl group, an n-hexyl group, and the like.

R¹ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbonatoms.

It is preferable that Y¹ to Y⁹ included in the polymerizable compoundaccording to one embodiment of the invention be independently a chemicalsingle bond, —O—, —O—C(═O)—, —C(═O)—O—, or —O—C(═O)—O—.

Each of G¹ and G² independently represents a substituted orunsubstituted divalent linear aliphatic group having 1 to 20 carbonatoms. Note that the expression “substituted or unsubstituted” usedherein in connection with a group or the like means that the group orthe like is unsubstituted, or substituted with a substituent(hereinafter the same).

Examples of the divalent linear aliphatic group having 1 to 20 carbonatoms include an alkylene group having 1 to 20 carbon atoms, such as amethylene group, an ethylene group, a trimethylene group, a propylenegroup, a tetramethylene group, a pentamethylene group, a hexamethylenegroup, an octamethylene group, and a decamethylene group (—(CH₂)₁₀—); analkenylene group having 2 to 20 carbon atoms, such as a vinylene group,a 1-methylvinylene group, a propenylene group, a 1-butenylene group, a2-butenylene group, a 1-pentenylene group, and a 2-pentenylene group;and the like.

Examples of a substituent that may substitute the divalent linearaliphatic group represented by G₁ and G₂ include a halogen atom such asa fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; analkoxy group having 1 to 6 carbon atoms, such as a methoxy group, anethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxygroup, a sec-butoxy group, a t-butoxy group, an n-pentyloxy group, andan n-hexyloxy group; and the like. Among these, a fluorine atom, amethoxy group, and an ethoxy group are preferable.

The linear aliphatic group optionally includes —O—, —S—, —O—C(O)—,—C(O)—O—, —O—C(═O)—O—, —NR²—C(═O)—, —C(═O)—NR²—, —NR²—, or —C(═O)—. Notethat a case where the linear aliphatic group includes two or morecontiguous —O— or —S— is excluded. R² is a hydrogen atom or an alkylgroup having 1 to 6 carbon atoms same as that represented by R¹, and ispreferably a hydrogen atom or a methyl group.

—O—, —O—C(═O)—, —C(═O)—O—, and —C(═O)— are preferable as the group thatis optionally included in the linear aliphatic group.

Specific examples of the linear aliphatic group that includes the abovegroup include —CH₂—CH₂—O—CH₂—CH₂—, —CH₂—CH₂—S—CH₂—CH₂—,—CH₂—CH₂—O—C(═O)—CH₂—CH₂—, —CH₂—CH₂—C(═O)—O—CH₂—CH₂—,—CH₂—CH₂—C(═O)—O—CH₂—, —CH₂—O—C(═O)—O—CH₂—CH₂—,—CH₂—CH₂—NR²—C(═O)—CH₂—CH₂—, —CH₂—CH₂—C(═O)—NR²—CH₂—, —CH₂—NR²—CH₂—CH₂—,—CH₂—C(═O)—CH₂—, and the like.

It is preferable that each of G¹ and G² be independently a substitutedor unsubstituted divalent linear aliphatic group having 1 to 12 carbonatoms that optionally includes —O—, —O—C(═O)—, —C(═O)—O—, or —C(═O)—,provided that a case where the aliphatic group includes two or morecontiguous —O— is excluded. It is more preferable that each of G¹ and G²be independently a divalent linear aliphatic group such as an alkylenegroup having 1 to 12 carbon atoms or an alkenylene group having 2 to 20carbon atoms, still more preferably an alkylene group having 1 to 12carbon atoms, and particularly preferably a tetramethylene group(—(CH₂)₄—), a hexamethylene group (—(CH₂)₆—), an octamethylene group(—(CH₂)₈—), or a decamethylene group (—(CH₂)₁₀—).

Each of Z¹ to Z³ independently represents an alkenyl group having 2 to10 carbon atoms that is substituted with a halogen atom, orunsubstituted.

The number of carbon atoms of the alkenyl group is preferably 2 to 6.Examples of the halogen atom that may substitute the alkenyl grouprepresented by Z¹ and Z² include a fluorine atom, a chlorine atom, abromine atom, and the like. Among these, a chlorine atom is preferable.

Specific examples of the alkenyl group having 2 to 10 carbon atomsrepresented by Z¹ to Z³ include CH₂═CH—, CH₂═C(CH₃)—, CH₂═CH—CH₂—,CH₃—CH═CH—, CH₂═CH—CH₂CH₂—, CH₂═C(CH₃)—CH₂CH₂—, (CH₃)₂C═CH—CH₂—,(CH₃)₂C═CH—CH₂CH₂—, CH₂═C(Cl)—, CH₂═C(CH₃)—CH₂—, CH₃—CH═CH—CH₂—, and thelike.

It is preferable that each of Z¹ to Z³ be independently CH₂═CH—,CH₂═C(CH₃)—, CH₂═C(Cl)—, CH₂═CH—CH₂—, CH₂═C(CH₃)—CH₂—, orCH₂═C(CH₃)—CH₂CH₂—, more preferably CH₂═CH—, CH₂═C(CH₃)—, or CH₂═C(Cl)—,and particularly preferably CH₂═CH—, in order to more advantageouslyachieve the intended effects of the invention.

A^(x) represents a group represented by the following formula (II). Notethat the symbol “-” in the formula (II) represents a bond from the ring(hereinafter the same).

wherein X represents —NR²—, an oxygen atom, a sulfur atom, —SO—, or—SO₂—, and R² represents a hydrogen atom or an alkyl group having 1 to 6carbon atoms same as that represented by R¹.

An arbitrary C—H included in the group represented by the formula (II)is optionally substituted with a nitrogen atom. Examples of the grouprepresented by the formula (II) in which an arbitrary C—H is substitutedwith a nitrogen atom include groups respectively represented by thefollowing formulas.

A^(x) is preferably a group among groups respectively represented by thefollowing formulas.

A^(x) is particularly preferably the group among groups respectivelyrepresented by the following formula.

D represents a substituted or unsubstituted alkylene group having 1 to20 carbon atoms, or a substituted or unsubstituted cycloalkanediyl grouphaving 3 to 20 carbon atoms.

The alkylene group having 1 to 20 carbon atoms optionally includes —O—,—S—, —O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, —NR³—C(═O)—, —C(═O)—NR³—, —NR³—,or —C(═O)—. Note that a case where the alkylene group includes two ormore contiguous —O— or —S— is excluded.

R³ represents a hydrogen atom or an alkyl group having 1 to 6 carbonatoms same as that represented by R¹.

Examples of the alkylene group having 1 to 20 carbon atoms (that issubstituted or unsubstituted) that may be represented by D include amethylene group, an ethylene group, an n-propylene group, anisopropylene group, an n-butylene group, an isobutylene group, a1-methylpentylene group, a 1-ethylpentylene group, a sec-butylene group,a t-butylene group, an n-pentylene group, an isopentylene group, aneopentylene group, an n-hexylene group, an isohexylene group, ann-heptylene group, an n-octylene group, an n-nonylene group, ann-decylene group, an n-undecylene group, an n-dodecylene group, ann-tridecylene group, an n-tetradecylene group, an n-pentadecylene group,an n-hexadecylene group, an n-heptadecylene group, an n-octadecylenegroup, an n-nonadecylene group, an n-icosylene group, and the like. Thenumber of carbon atoms of the substituted or unsubstituted alkylenegroup having 1 to 20 carbon atoms is preferably 1 to 12, and morepreferably 4 to 10.

Examples of a substituent that may substitute the substituted orunsubstituted alkylene group having 1 to 20 carbon atoms represented byD include a halogen atom such as a fluorine atom and a chlorine atom; acyano group; a substituted amino group such as a dimethylamino group; analkoxy group having 1 to 20 carbon atoms, such as a methoxy group, anethoxy group, an isopropoxy group, and a butoxy group; an alkoxy grouphaving 1 to 12 carbon atoms that is substituted with an alkoxy grouphaving 1 to 12 carbon atoms, such as a methoxymethoxy group and amethoxyethoxy group; a nitro group; an aryl group such as a phenyl groupand a naphthyl group; a cycloalkyl group having 3 to 8 carbon atoms,such as a cyclopropyl group, a cyclopentyl group, and a cyclohexylgroup; a cycloalkyloxy group having 3 to 8 carbon atoms, such as

a cyclopentyloxy group and a cyclohexyloxy group; a cyclic ether grouphaving 2 to 12 carbon atoms, such as a tetrahydrofuranyl group, atetrahydropyranyl group,a dioxoranyl group, and a dioxanyl group; an aryloxy group having 6 to14 carbon atoms, such as a phenoxy group and a naphthoxy group; afluoroalkoxy group having 1 to 12 carbon atoms in which at least onehydrogen atom is substituted with a fluorine atom, such as atrifluoromethyl group, a pentafluoroethyl group, anda 2,2,2-trifluoroethyl group; a benzofuryl group; a benzopyranyl group;a benzodioxolyl group; a benzodioxanyl group; —SO₂R⁴; —C(═O)—R⁵;—C(═O)—OR⁵; —SR⁵; an alkoxy group having 1 to 12 carbon atoms that issubstituted with —SR⁵; a hydroxyl group; and the like. Note that R⁴represents an alkyl group having 1 to 12 carbon atoms, an alkenyl grouphaving 2 to 12 carbon atoms, a phenyl group, or a 4-methylphenyl group,and R⁵ represents an alkyl group having 1 to 12 carbon atoms, an alkenylgroup having 2 to 12 carbon atoms,a cycloalkyl group having 3 to 12 carbon atoms, or an aromatichydrocarbon group having 6 to 12 carbon atoms.

Examples of the cycloalkanediyl group having 3 to 20 carbon atoms (thatis substituted or unsubstituted) that may be represented by D include acyclopropanediyl group; a cyclobutanediyl group such as acyclobutane-1,2-diyl group and a cyclobutane-1,3-diyl group; acyclopentanediyl group such as a cyclopentane-1,2-diyl group and acyclopentane-1,3-diyl group; a cyclohexanediyl group such as acyclohexane-1,2-diyl group, a cyclohexane-1,3-diyl group, and acyclohexane-1,4-diyl group; a cycloheptanediyl group such as acycloheptane-1,2-diyl group, a cycloheptane-1,3-diyl group, and acycloheptane-1,4-diyl group; a cyclooctanediyl group such as acyclooctane-1,2-diyl group, a cyclooctane-1,3-diyl group, acyclooctane-1,4-diyl group, and a cyclooctane-1,5-diyl group; acyclodecanediyl group such as a cyclodecane-1,2-diyl group, acyclodecane-1,3-diyl group, a cyclodecane-1,4-diyl group, and acyclodecane-1,5-diyl group; a cyclododecanediyl group such as acyclododecane-1,2-diyl group, a cyclododecane-1,3-diyl group, acyclododecane-1,4-diyl group, and a cyclododecane-1,5-diyl group; acyclotetradecanediyl group such as a cyclotetradecane-1,2-diyl group, acyclotetradecane-1,3-diyl group, a cyclotetradecane-1,4-diyl group, acyclotetradecane-1,5-diyl group, and a cyclotetradecane-1,7-diyl group;a cycloeicosanediyl group such as a cycloeicosane-1,2-diyl group and acycloeicosane-1,10-diyl group; and the like.

The cycloalkanediyl group having 3 to 30 carbon atoms that may berepresented by D is classified into a cis-stereoisomer and atrans-stereoisomer that differ in the steric configuration of the carbonatoms bonded to N and Y⁹.

The cycloalkanediyl group may be a cis-isomer, a trans-isomer, or amixture including a cis-isomer and a trans-isomer.

Examples of a substituent that may substitute the cycloalkanediyl grouphaving 3 to 20 carbon atoms that may be represented by D include ahalogen atom such as a fluorine atom and a chlorine atom; a cyano group;a substituted amino group such as a dimethylamino group; an alkyl grouphaving 1 to 6 carbon atoms, such as a methyl group, an ethyl group, anda propyl group; an alkoxy group having 1 to 6 carbon atoms, such as amethoxy group, an ethoxy group, and an isopropoxy group; a nitro group;an aryl group such as a phenyl group and a naphthyl group; a cycloalkylgroup having 3 to 8 carbon atoms, such as a cyclopropyl group, acyclopentyl group, and a cyclohexyl group; —C(═O)—R⁵; —C(═O)—OR⁵;—SO₂R⁴; a hydroxyl group; and the like. Note that R⁴ and R⁵ are the sameas defined above.

It is preferable that D be a substituted or unsubstituted alkylene grouphaving 1 to 20 carbon atoms that optionally includes —O—, —S—,—O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, or —C(═O)— (provided that a casewhere the alkylene group includes two or more contiguous —O— or —S— isexcluded), more preferably a substituted or unsubstituted alkylene grouphaving 1 to 20 carbon atoms, still more preferably an alkylene grouphaving 1 to 20 carbon atoms, and particularly preferably an alkylenegroup having 1 to 6 carbon atoms.

A¹ represents a substituted or unsubstituted trivalent aromatic group.The trivalent aromatic group may be a trivalent carbocyclic aromaticgroup, or may be a trivalent heterocyclic aromatic group. It ispreferable that the trivalent aromatic group be a trivalent carbocyclicaromatic group, more preferably a trivalent benzene ring group or atrivalent naphthalene ring group, and still more preferably a groupamong a trivalent benzene ring group and trivalent naphthalene ringgroups respectively represented by the following formulas, in order tomore advantageously achieve the intended effects of the invention.

Note that the substituents Y¹ and Y² are also included in the followingformulas so that the bonding state can be easily understood (Y¹ and Y²are the same as defined above; hereinafter the same).

A¹ is more preferably a group among groups respectively represented bythe following formulas (A11) to (A25), still more preferably a groupamong the groups respectively represented by the formulas (A11), (A13),(A15), (A19), and (A23), and particularly preferably the grouprepresented by the formula (A11) or the group represented by the formula(A23).

Examples of a substituent that may substitute the trivalent aromaticgroup represented by A¹ include a halogen atom such as a fluorine atomand a chlorine atom; a cyano group; an alkyl group having 1 to 6 carbonatoms, such as a methyl group, an ethyl group, and a propyl group; analkenyl group having 2 to 6 carbon atoms, such as a vinyl group and anallyl group; an alkyl halide group having 1 to 6 carbon atoms, such as atrifluoromethyl group; a substituted amino group such as a dimethylaminogroup; an alkoxy group having 1 to 6 carbon atoms, such as a methoxygroup, an ethoxy group, and an isopropoxy group; a nitro group; an arylgroup such as a phenyl group and a naphthyl group; —C(═O)—R⁶;—C(═O)—OR⁶; —SO₂R⁶; and the like. Note that R⁶ is an alkyl group having1 to 6 carbon atoms (e.g., methyl group or ethyl group), or an arylgroup having 6 to 14 carbon atoms (e.g., phenyl group). It is preferablethat A¹ be unsubstituted.

Each of A² and A³ independently represents a substituted orunsubstituted divalent alicyclic hydrocarbon group having 3 to 30 carbonatoms.

Examples of the divalent alicyclic hydrocarbon group having 3 to 30carbon atoms include a cycloalkanediyl group having 3 to 30 carbonatoms, a divalent fused alicyclic group having 10 to 30 carbon atoms,and the like.

Examples of the cycloalkanediyl group having 3 to 30 carbon atomsinclude a cyclopropanediyl group; a cyclobutanediyl group such as acyclobutane-1,2-diyl group and a cyclobutane-1,3-diyl group; acyclopentanediyl group such as

a cyclopentane-1,2-diyl group and a cyclopentane-1,3-diyl group; acyclohexanediyl group such as a cyclohexane-1,2-diyl group, acyclohexane-1,3-diyl group, and a cyclohexane-1,4-diyl group; acycloheptanediyl group such as a cycloheptane-1,2-diyl group, acycloheptane-1,3-diyl group, and a cycloheptane-1,4-diyl group;a cyclooctanediyl group such as a cyclooctane-1,2-diyl group, acyclooctane-1,3-diyl group, a cyclooctane-1,4-diyl group, and acyclooctane-1,5-diyl group;a cyclodecanediyl group such as a cyclodecane-1,2-diyl group, acyclodecane-1,3-diyl group, a cyclodecane-1,4-diyl group, and acyclodecane-1,5-diyl group;a cyclododecanediyl group such as a cyclododecane-1,2-diyl group,a cyclododecane-1,3-diyl group, a cyclododecane-1,4-diyl group, anda cyclododecane-1,5-diyl group; a cyclotetradecanediyl group such asa cyclotetradecane-1,2-diyl group, a cyclotetradecane-1,3-diyl group,a cyclotetradecane-1,4-diyl group, a cyclotetradecane-1,5-diyl group,anda cyclotetradecane-1,7-diyl group; a cycloeicosanediyl group such asa cycloeicosane-1,2-diyl group and a cycloeicosane-1,10-diyl group; andthe like.

Examples of the divalent fused alicyclic group having 10 to 30 carbonatoms include a decalindiyl group such as a decalin-2,5-diyl group and adecalin-2,7-diyl group; an adamantanediyl group such as anadamantane-1,2-diyl group and an adamantane-1,3-diyl group; abicyclo[2.2.1]heptanediyl group such as a bicyclo[2.2.1]heptane-2,3-diylgroup, a bicyclo[2.2.1]heptane-2,5-diyl group, and abicyclo[2.2.1]heptane-2,6-diyl group; and the like.

These divalent alicyclic hydrocarbon groups may be substituted with asubstituent at an arbitrary position. Examples of the substituent arethe same as those mentioned above in connection with the aromatic grouprepresented by A¹.

A² and A³ are preferably a divalent alicyclic hydrocarbon group having 3to 12 carbon atoms, more preferably a cycloalkanediyl group having 3 to12 carbon atoms, still more preferably a group among the groupsrespectively represented by the following formulas (A31) to (A34), andparticularly preferably the group represented by the formula (A32).

The divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms isclassified into a cis-stereoisomer and a trans-stereoisomer that differin the steric configuration of the carbon atoms bonded to Y¹ and Y³ (orY² and Y⁴). For example, a cyclohexane-1,4-diyl group is classified intoa cis-isomer (A32a) and a trans-isomer (A32b) (see below).

The divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms maybe a cis-isomer, a trans-isomer, or a mixture including a cis-isomer anda trans-isomer. Note that it is preferable that the divalent alicyclichydrocarbon group having 3 to 30 carbon atoms be a trans-isomer or acis-isomer, and more preferably a trans-isomer, since an excellentalignment capability can be obtained.

Each of A⁴ and A⁵ independently represents a substituted orunsubstituted divalent aromatic group having 4 to 30 carbon atoms.

The aromatic group represented by A⁴ and A⁵ may be a monocyclic aromaticgroup, or may be a polycyclic aromatic group.

Specific examples of a preferable aromatic group represented by A⁴ andA⁵ include the groups respectively represented by the followingformulas.

The divalent aromatic group represented by A⁴ and A⁵ may be substitutedwith a substituent at an arbitrary position.

Examples of the substituent include a halogen atom, a cyano group, ahydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxygroup having 1 to 6 carbon atoms, a nitro group, a —C(═O)—OR⁷ group, andthe like. Note that R⁷ is an alkyl group having 1 to 6 carbon atoms.Among these, a halogen atom, an alkyl group having 1 to 6 carbon atoms,and an alkoxy group having 1 to 6 carbon atoms are preferable as thesubstituent. A fluorine atom is preferable as the halogen atom. A methylgroup, an ethyl group, and a propyl group are preferable as the alkylgroup having 1 to 6 carbon atoms. A methoxy group and an ethoxy groupare preferable as the alkoxy group having 1 to 6 carbon atoms.

It is preferable that each of A⁴ and A⁵ be independently a group amongthe groups respectively represented by the following formulas (A41),(A42), and (A43) that are optionally substituted with a substituent, andparticularly preferably the group represented by the formula (A41) thatis optionally substituted with a substituent, in order to moreadvantageously achieve the intended effects of the invention.

Q¹ is a hydrogen atom, or a substituted or unsubstituted alkyl grouphaving 1 to 6 carbon atoms.

Examples of the substituted or unsubstituted alkyl group having 1 to 6carbon atoms are the same as those mentioned above in connection withR¹.

It is preferable that Q¹ be a hydrogen atom or an alkyl group having 1to 6 carbon atoms, and more preferably a hydrogen atom or a methylgroup.

Each of m and n is independently 0 or 1. It is preferable that both mand n be 0.

The polymerizable compound according to one embodiment of the inventionmay be produced by effecting the following reaction, for example.

wherein Y¹ to Y⁸, G¹, G², Z¹ to Z³, A^(x), D, A¹ to A⁵, Q¹, m, and n arethe same as defined above, L is a leaving group (e.g., hydroxyl group,halogen atom, methanesulfonyloxy group, or p-toluenesulfonyloxy group),and —Y^(9a) is a group that reacts with L to form —Y⁹—.

Specifically, the polymerizable compound according to one embodiment ofthe invention that is represented by the formula (I) can be produced byreacting the hydrazine compound represented by the formula (3)(hydrazine compound (3)) with the carbonyl compound represented by theformula (4) (carbonyl compound (4)) in a molar ratio (hydrazine compound(3):carbonyl compound (4)) of 1:2 to 2:1 (preferably 1:1.5 to 1.5:1) toobtain the compound represented by the formula (II) (compound (II)), andreacting the compound (II) with the compound represented by the formula(5) (compound (5)) in a molar ratio (compound (II):compound (5)) of 1:1to 1:2 (preferably 1:1.1 to 1:1.5).

The reaction that synthesizes the compound (II) is preferably effectedin the presence of an acid catalyst such as an organic acid (e.g.,(±)-10-camphorsulfonic acid or p-toluenesulfonic acid), or an inorganicacid (e.g., hydrochloric acid or sulfuric acid). The addition of theacid catalyst may reduce the reaction time, and improve the yield. Theacid catalyst is normally added in an amount of 0.001 to 1 mol based on1 mol of the carbonyl compound (4). The acid catalyst may be addeddirectly, or a solution prepared by dissolving the acid catalyst in anappropriate solvent may be added.

A solvent used for the above reaction is not particularly limited aslong as the solvent is inert to the reaction. Examples of the solventinclude an alcohol-based solvent such as methyl alcohol, ethyl alcohol,n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol,sec-butyl alcohol, and t-butyl alcohol; an ether-based solvent such asdiethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, 1,4-dioxane, andcyclopentyl methyl ether; an ester-based solvent such as ethyl acetate,propyl acetate, and methyl propionate; an aromatic hydrocarbon-basedsolvent such as benzene, toluene, and xylene; an aliphatichydrocarbon-based solvent such as n-pentane, n-hexane, and n-heptane; anamide-based solvent such as N,N-dimethylformamide, N-methylpyrrolidone,and hexamethylphosphoric acid triamide; a sulfur-containing solvent suchas dimethyl sulfoxide and sulfolane; a mixed solvent including two ormore solvents among these solvents; and the like.

Among these, an alcohol-based solvent, an ether-based solvent, and amixed solvent including an alcohol-based solvent and an ether-basedsolvent are preferable.

The solvent may be used in an appropriate amount taking account of thetype of each compound, the reaction scale, and the like. The solvent isnormally used in an amount of 1 to 100 g per gram of the hydrazinecompound (3).

The reaction proceeds smoothly when the reaction temperature is setwithin the range from −10° C. to the boiling point of the solvent. Thereaction time is selected taking account of the reaction scale, but isnormally several minutes to several hours.

The compound (II) is then reacted with the compound (5) to obtain thetarget product.

A combination of the compound (II) and the compound (5) (i.e., acombination of the group -L included in the compound (II) and the group—Y^(9a) included in the compound (5) that take part in the reaction) maybe appropriately selected taking account of the target product.

For example, when producing the compound represented by the formula (I)in which —Y⁹— is —O—C(═O)— (compound (Ia)), the reaction is effectedusing the compound (II) in which L is a hydroxyl group (compound (IIa))and the compound (5) in which —Y^(9a) is —C(═O)X^(a) (acid halide (5a)).Note that X^(a) is a halogen atom (e.g., chlorine atom or bromine atom).

wherein Y¹ to Y⁸, G¹, G², Z¹ to Z³, A^(x), A¹ to A⁵, Q¹, X^(a), D, m,and n are the same as defined above.

The compound (IIa) and the compound (5a) are preferably reacted in thepresence of a base such as triethylamine. The base is normally used inan amount of 1 to 3 mol based on 1 mol of the compound (IIa).

A solvent used for the above reaction is not particularly limited aslong as the solvent is inert to the reaction. Examples of the solventinclude those mentioned above in connection with the solvent used whenreacting the compound (4) and the compound (3).

The hydrazine compound (3) may be produced as described below.

wherein A^(x), D, and L are the same as defined above, and X^(b)represents a leaving group (e.g., halogen atom, methanesulfonyloxygroup, or p-toluenesulfonyloxy group).

Specifically the compound represented by the formula (2) (compound (2))is reacted with the hydrazine compound (1) in an appropriate solvent ina molar ratio (compound (2):compound (1)) of 1:1 to 1:20 (preferably 1:2to 1:10) to obtain the corresponding hydrazone compound (3).

A solvent used for the above reaction is not particularly limited aslong as the solvent is inert to the reaction. Examples of the solventinclude an alcohol-based solvent such as methyl alcohol, ethyl alcohol,n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol,sec-butyl alcohol, and t-butyl alcohol; an ether-based solvent such asdiethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, 1,4-dioxane, andcyclopentyl methyl ether; an aromatic hydrocarbon-based solvent such asbenzene, toluene, and xylene; an aliphatic hydrocarbon-based solventsuch as n-pentane, n-hexane, and n-heptane; an amide-based solvent suchas N,N-dimethylformamide, N-methylpyrrolidone, and hexamethylphosphoricacid triamide; a sulfur-containing solvent such as dimethyl sulfoxideand sulfolane; a mixed solvent including two or more solvents amongthese solvents; and the like.

Among these, an alcohol-based solvent, an ether-based solvent, and amixed solvent including an alcohol-based solvent and an ether-basedsolvent are preferable.

The solvent may be used in an appropriate amount taking account of thetype of each compound, the reaction scale, and the like. The solvent isnormally used in an amount of 1 to 100 g per gram of hydrazine.

The reaction proceeds smoothly when the reaction temperature is setwithin the range from −10° C. to the boiling point of the solvent. Thereaction time is selected taking account of the reaction scale, but isnormally several minutes to several hours.

The carbonyl compound (4) may be produced by appropriately bonding andmodifying a plurality of known compounds having a desired structure byarbitrarily combining an ether linkage (—O—)-forming reaction, an esterlinkage (—C(═O)—O— or —O—C(═O)—)-forming reaction, a carbonate linkage(—O—C(═O)—O—)-forming reaction, and an amide linkage (—C(═O)—NH— or—NH—C(═O)—)-forming reaction.

An ether linkage may be formed as described below.

(i) A compound represented by D1-hal (wherein hal is a halogen atom(hereinafter the same)) and a compound represented by D2-OMet (whereinMet is an alkali metal (mainly sodium) (hereinafter the same)) are mixedand condensed (Williamson synthesis). Note that D1 and D2 are anarbitrary organic group (hereinafter the same).(ii) A compound represented by D1-hal and a compound represented byD2-OH are mixed and condensed in the presence of a base (e.g., sodiumhydroxide or potassium hydroxide).(iii) A compound represented by D1-J (wherein J is an epoxy group) and acompound represented by D2-OH are mixed and condensed in the presence ofa base (e.g., sodium hydroxide or potassium hydroxide).(iv) A compound represented by D1-OFN (wherein OFN is a group thatincludes an unsaturated bond) and a compound represented by D2-OMet aremixed and subjected to an addition reaction in the presence of a base(e.g., sodium hydroxide or potassium hydroxide).(v) A compound represented by D1-hal and a compound represented byD2-OMet are mixed and condensed in the presence of copper or cuprouschloride (Ullmann condensation).

An ester linkage and an amide linkage may be formed as described below.

(vi) A compound represented by D1-COOH and a compound represented byD2-OH or D2-NH₂ are subjected to dehydration and condensation in thepresence of a dehydration-condensation agent (e.g.,N,N-dicyclohexylcarbodiimide).(vii) A compound represented by D1-COOH is reacted with a halogenatingagent to obtain a compound represented by D1-CO-hal, and the compoundrepresented by D1-CO-hal is reacted with a compound represented by D2-OHor D2-NH2 in the presence of a base.(viii) A compound represented by D1-COOH is reacted with an acidanhydride to obtain a mixed acid anhydride, and the mixed acid anhydrideis reacted with a compound represented by D2-OH or D2-NH₂.(ix) A compound represented by D1-COOH and a compound represented byD2-OH or D2-NH₂ are subjected to dehydration and condensation in thepresence of an acid catalyst or a base catalyst.

More specifically, the carbonyl compound (4) may be produced using thefollowing method (see the following reaction formula).

wherein Y¹ to Y⁸, G¹, G², Z¹, Z², A¹ to A⁵, and Q¹ are the same asdefined above, L¹ and L² are a leaving group (e.g., hydroxyl group,halogen atom, methanesulfonyloxy group, or p-toluenesulfonyloxy group),—Y^(1a) is a group that reacts with -L¹ to form —Y¹—, and —Y^(2a) is agroup that reacts with -L² to form —Y²—.

Specifically, the carbonyl compound (4) according to one embodiment ofthe invention may be produced by sequentially reacting the compoundrepresented by the formula (7a) and the compound represented by theformula (7b) with the compound represented by the formula (6d) using anether linkage (—O—)-forming reaction, an ester linkage (—C(═O)—O— or—O—C(═O)—)-forming reaction, or a carbonate linkage(—O—C(═O)—O—)-forming reaction known in the art.

The carbonyl compound (4) in which Y¹ is a group represented byY¹¹—C(═O)—O—, and the group represented byZ²—Y⁸-G²-Y⁶-A⁵-(Y⁴-A³)_(n)-Y²— is identical with the group representedby Z¹—Y⁷-G¹-Y⁵-A⁴-(Y³-A²)_(m)-Y¹— (hereinafter referred to as “compound(4′)”) may be produced as shown below.

wherein Y³, Y⁵, Y⁷, G¹, Z¹, A¹, A², A⁴, Q¹, m, and L¹ are the same asdefined above, Y¹¹ is a group whereby Y¹ is represented by Y¹¹—C(═O)—O—,and Y¹ is the same as defined above.

Specifically, the dihydroxy compound represented by the formula (6)(compound (6)) is reacted with the compound represented by the formula(7) (compound (7)) in a molar ratio (compound (6):compound (7)) of 1:2to 1:4 (preferably 1:2 to 1:3) to produce the target compound (4′) withhigh selectivity in high yield.

When the compound (7) is a compound (carboxylic acid) represented by theformula (7) in which L¹ is a hydroxyl group, the target product may beobtained by effecting the reaction in the presence of adehydration-condensation agent (e.g.,1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride ordicyclohexylcarbodiimide).

The dehydration-condensation agent is normally used in an amount of 1 to3 mol based on 1 mol of the compound (7).

When the compound (7) is a compound (carboxylic acid) represented by theformula (7) wherein L¹ is a hydroxyl group, the target product may alsobe obtained by effecting the reaction in the presence of a sulfonylhalide (e.g., methanesulfonyl chloride or p-toluenesulfonyl chloride)and a base (e.g., triethylamine, diisopropylethylamine, pyridine, or4-(dimethylamino)pyridine).

The sulfonyl halide is normally used in an amount of 1 to 3 mol based on1 mol of the compound (7).

The base is normally used in an amount of 1 to 3 mol based on 1 mol ofthe compound (7).

In this case, the compound (mixed acid anhydride) represented by theformula (7) in which L¹ is a sulfonyloxy group may be isolated, andsubjected to the subsequent reaction.

When the compound (7) is a compound (acid halide) represented by theformula (7) in which L¹ is a halogen atom, the target product may beobtained by effecting the reaction in the presence of a base.

Examples of the base include an organic base such as triethylamine andpyridine; and an inorganic base such as sodium hydroxide, sodiumcarbonate, and sodium hydrogen carbonate.

The base is normally used in an amount of 1 to 3 mol based on 1 mol ofthe compound (7).

Examples of the solvent used for the above reaction include achlorine-based solvent such as chloroform and methylene chloride; anamide-based solvent such as N-methylpyrrolidone, N,N-dimethylformamide,N,N-dimethylacetamide, and hexamethylphosphoric triamide; an ether-basedsolvent such as 1,4-dioxane, cyclopentyl methyl ether, tetrahydrofuran,tetrahydropyran, and 1,3-dioxolane; a sulfur-containing solvent such asdimethyl sulfoxide and sulfolane; an aromatic hydrocarbon-based solventsuch as benzene, toluene, and xylene; an aliphatic hydrocarbon-basedsolvent such as n-pentane, n-hexane, and n-octane; an alicyclichydrocarbon-based solvent such as cyclopentane and cyclohexane; a mixedsolvent including two or more solvents among these solvents; and thelike.

The solvent may be used in an appropriate amount taking account of thetype of each compound, the reaction scale, and the like. The solvent isnormally used in an amount of 1 to 50 g per gram of the hydroxy compound(6).

Many of the compounds (6) are known compounds, and may be produced usinga known method.

For example, the compound (6) may be produced using the following method(see the following reaction formula) (see WO2009/042544 and The Journalof Organic Chemistry, 2011, 76, 8082-8087). A commercially availableproduct may be used as the compound (6) either directly or afterpurification.

wherein A¹ and Q¹ are the same as defined above, A^(1a) is a divalentaromatic group that forms A¹ through formylation or acylation, and R¹ isa protecting group for a hydroxyl group, such as an alkyl group having 1to 6 carbon atoms (e.g., methyl group or ethyl group), or an alkoxyalkylgroup having 2 to 6 carbon atoms (e.g., methoxymethyl group).

Specifically, the target compound (6) may be produced by alkylating thehydroxyl groups of the dihydroxy compound represented by the formula(6a) (e.g., 1,4-dihydroxybenzene or 1,4-dihydroxynaphthalene) to obtainthe compound represented by the formula (6b), effecting formylation oracylation at the ortho position with respect to the OR′ group using aknown method to obtain the compound represented by the formula (6c), anddeprotecting (dealkylating) the compound represented by the formula(6c).

A commercially available product may be used as the compound (6) eitherdirectly or after purification.

Most of the compounds (7) are known compounds. The compound (7) may beproduced by appropriately bonding and modifying a plurality of knowncompounds having a desired structure by arbitrarily combining an etherlinkage (—O—)-forming reaction, an ester linkage (—C(═O)—O— or—O—C(═O)—)-forming reaction, a carbonate linkage (—O—C(═O)—O—)-formingreaction, and an amide linkage (—C(═O)—NH— or —NH—C(═O)—)-formingreaction.

For example, when the compound (7) is a compound represented by thefollowing formula (7′) (compound (7′)), the compound (7) may be producedas shown below using a dicarboxylic acid represented by the formula (9′)(compound (9′)).

wherein Y⁵, Y⁷, G¹, Z¹, A², A⁴, and Y¹¹ are the same as defined above,Y¹² is a group whereby Y³ is represented by —O—C(═O)—Y¹², and Rrepresents an alkyl group (e.g., methyl group or ethyl group) or asubstituted or unsubstituted aryl group (e.g., phenyl group orp-methylphenyl group).

Specifically, the sulfonyl chloride represented by the formula (10) isreacted with the compound (9′) in the presence of a base (e.g.,triethylamine or 4-(dimethylamino)pyridine).

The compound (8) and a base (e.g., triethylamine or4-(dimethylamino)pyridine) are added to the reaction mixture to effect areaction.

Sulfonyl chloride is normally used in an amount of 0.5 to 0.7equivalents based on 1 equivalent of the compound (9′).

The compound (8) is normally used in an amount of 0.5 to 0.6 equivalentsbased on 1 equivalent of the compound (9′).

The base is normally used in an amount of 0.5 to 0.7 equivalents basedon 1 equivalent of the compound (3).

The reaction temperature is set to 20 to 30° C. The reaction time isdetermined taking account of the reaction scale and the like, but isnormally several minutes to several hours.

Examples of a solvent used for the above reaction include thosementioned above in connection with the solvent that may be used whenproducing the compound (4′). It is preferable to use an ether as thesolvent.

The solvent may be used in an appropriate amount taking account of thetype of each compound, the reaction scale, and the like. The solvent isnormally used in an amount of 1 to 50 g per gram of the compound (9′).

The target product is isolated by performing a post-treatment operationnormally employed in synthetic organic chemistry after completion of thereaction, optionally followed by a known purification/separation meanssuch as column chromatography, recrystallization, or distillation.

The structure of the target product may be identified bymeasurement/elemental analysis (e.g., NMR spectrometry, IR spectrometry,or mass spectrometry), and the like.

2) Polymerizable Composition

A polymerizable composition according to one embodiment of the inventionincludes the polymerizable compound according to one embodiment of theinvention, and an initiator. The initiator is used to more efficientlypolymerize the polymerizable compound according to one embodiment of theinvention.

The initiator may be appropriately selected taking account of the typeof polymerizable group included in the polymerizable compound. Forexample, a radical initiator may be used when the polymerizable group isa radically polymerizable group, an anionic initiator may be used whenthe polymerizable group is an anionically polymerizable group, and acationic initiator may be used when the polymerizable group is acationically polymerizable group.

Examples of the radical initiator include a thermal radical generatorthat is a compound that generates active species that initiate thepolymerization of the polymerizable compound upon heating, and aphoto-radical generator that is a compound that generates active speciesthat initiate the polymerization of the polymerizable compound uponexposure to exposure light (e.g., visible light, ultraviolet rays (e.g.,i-line), deep ultraviolet rays, electron beams, or X-rays). It ispreferable to use the photo-radical generator.

Examples of the photo-radical generator include an acetophenone-basedcompound, a biimidazole-based compound, a triazine-based compound, anO-acyloxime-based compound, an onium salt-based compound, abenzoin-based compound, a benzophenone-based compound, anα-diketone-based compound, a polynuclear quinone-based compound, axanthone-based compound, a diazo-based compound, an imidesulfonate-based compound, and the like. These compounds generate eitheror both of active radicals and an active acid upon exposure. Thesephoto-radical generators may be used either alone or in combination.

Specific examples of the acetophenone-based compound include2-hydroxy-2-methyl-1-phenylpropan-1-one,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one,1-hydroxycyclohexyl phenyl ketone,2,2-dimethoxy-1,2-diphenylethan-1-one, 1,2-octanedione,2-benzyl-2-dimethylamino-4′-morpholinobutyrophenone, and the like.

Specific examples of the biimidazole-based compound include2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetrakis(4-ethoxycarbonylphenyl)-1,2′-biimidazole,2,2′-bis(2-bromophenyl)-4,4′,5,5′-tetrakis(4-ethoxycarbonylphenyl)-1,2′-biimidazole,2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole,2,2′-bis(2,4-dichlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole,2,2′-bis(2,4,6-trichlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole,2,2′-bis(2-bromophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole,2,2′-bis(2,4-dibromophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole,2,2′-bis(2,4,6-tribromophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole,and the like.

When using a biimidazole-based compound as a photoinitiator, it ispreferable to use a hydrogen donor in combination with thebiimidazole-based compound in order to further improve sensitivity.

The term “hydrogen donor” used herein refers to a compound that candonate a hydrogen atom to radicals generated by the biimidazole-basedcompound upon exposure. A mercaptan-based compound, an amine-basedcompound, and the like are preferable as the hydrogen donor.

Examples of the mercaptan-based compound include2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole,2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-2,5-dimethylaminopyridine,and the like. Examples of the amine-based compound include4,4′-bis(dimethylamino)benzophenone, 4,4′-bis(diethylamino)benzophenone,4-diethylaminoacetophenone, 4-dimethylaminopropiophenone,ethyl-4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid,4-dimethylaminobenzonitrile, and the like.

Specific examples of the triazine-based compound include atriazine-based compound that includes a halomethyl group, such as

-   2,4,6-tris(trichloromethyl)-s-triazine,    2-methyl-4,6-bis(trichloromethyl)-s-triazine,-   2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine,-   2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine,-   2-[2-(4-diethylamino-2-methylphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine,-   2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine,-   2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine,-   2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, and-   2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine.

Specific examples of the O-acyloxime-based compound include

-   1-[4-(phenylthio)phenyl]-heptane-1,2-dione-2-(O-benzoyloxime),-   1-[4-(phenylthio)phenyl]-octane-1,2-dione-2-(O-benzoyloxime),-   1-[4-(benzoyl)phenyl]-octane-1,2-dione-2-(O-benzoyloxime),-   1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethanone-1-(O-acetyloxime),-   1-[9-ethyl-6-(3-methylbenzoyl)-9H-carbazol-3-yl]-ethanone-1-(O-acetyloxime),-   1-(9-ethyl-6-benzoyl-9H-carbazol-3-yl)-ethanone-1-(O-acetyloxime),-   ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime),-   ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime),-   ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime),-   ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime),-   ethanone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)benzoyl}-9H-carbazol-3-yl]-1-(O-acetyloxime),-   ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime),-   ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxybenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime),-   ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylmethoxybenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime),-   ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime),    ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylmethoxybenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime),-   ethanone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9H-carbazol-3-yl]-1-(O-acetyloxime),    and the like.

A commercially available product may be used directly as thephoto-radical generator. Specific examples of a commercially availableproduct that may be used as the photo-radical generator include Irgacure907, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 819, Irgacure907, and Irgacure OXE02 (manufactured by BASF); Adekaoptomer N1919(manufactured by Adeka Corporation); and the like.

Examples of the anionic initiator include an alkyllithium compound; amonolithium salt or a monosodium salt of biphenyl, naphthalene, pyrene,and the like; a polyfunctional initiator such as a dilithium salt and atrilithium salt; and the like.

Examples of the cationic initiator include a proton acid such assulfuric acid, phosphoric acid, perchloric acid, andtrifluoromethanesulfonic acid; a Lewis acid such as boron trifluoride,aluminum chloride, titanium tetrachloride, and tin tetrachloride; anaromatic onium salt or a combination of an aromatic onium salt and areducing agent; and the like.

These initiators may be used either alone or in combination.

The initiator is normally used to prepare the polymerizable compositionaccording to one embodiment of the invention in a ratio of 0.1 to 30parts by weight, and preferably 0.5 to 10 parts by weight, based on 100parts by weight of the polymerizable compound.

It is preferable to add a surfactant to the polymerizable compositionaccording to one embodiment of the invention in order to adjust thesurface tension of the polymerizable composition. The surfactant is notparticularly limited. A nonionic surfactant is normally preferable asthe surfactant. A commercially available product may be used as thenonionic surfactant. Examples of a commercially available product thatmay be used as the nonionic surfactant include an oligomer having amolecular weight of about several thousand (e.g., “KH-40” manufacturedby AGC Seimi Chemical Co., Ltd.), and the like. The surfactant isnormally added to the polymerizable composition according to oneembodiment of the invention in a ratio of 0.01 to 10 parts by weight,and preferably 0.1 to 2 parts by weight, based on 100 parts by weight ofthe polymerizable compound.

The polymerizable composition according to one embodiment of theinvention may further include an additional additive such as anadditional copolymerizable monomer (described later), a metal, a metalcomplex, a dye, a pigment, a fluorescent material, a phosphorescentmaterial, a leveling agent, a thixotropic agent, a gelling agent, apolysaccharide, a UV absorber, an IR (infrared) absorber, anantioxidant, an ion-exchange resin, and a metal oxide (e.g., titaniumoxide). Each additive is normally added to the polymerizable compositionaccording to one embodiment of the invention in a ratio of 0.1 to 20parts by weight based on 100 parts by weight of the polymerizablecompound.

The polymerizable composition according to one embodiment of theinvention may be prepared by mixing and dissolving given amounts of thepolymerizable compound according to one embodiment of the invention, theinitiator, and an optional additive in an appropriate organic solvent.

Examples of the organic solvent include a ketone such as cyclopentanone,cyclohexanone, and methyl ethyl ketone; an acetate such as butyl acetateand amyl acetate; a halogenated hydrocarbon such as chloroform,dichloromethane, and dichloroethane; an ether such as 1,4-dioxane,cyclopentyl methyl ether, tetrahydrofuran, tetrahydropyran, and1,3-dioxolane; and the like.

The polymerizable composition thus obtained is useful as a material forproducing a polymer according to one embodiment of the invention, orproducing an optically anisotropic product according to one embodimentof the invention (described below).

3) Polymer

A polymer according to one embodiment of the invention is (1) a polymerobtained by polymerizing the polymerizable compound according to oneembodiment of the invention, or (2) a polymer obtained by polymerizingthe polymerizable composition according to one embodiment of theinvention.

The term “polymerization” used herein refers to a chemical reaction in abroad sense including a normal polymerization reaction and acrosslinking reaction.

(1) Polymer Obtained by Polymerizing Polymerizable Compound

The polymer obtained by polymerizing the polymerizable compoundaccording to one embodiment of the invention may be a homopolymer of thepolymerizable compound according to one embodiment of the invention, acopolymer of two or more types of the polymerizable compound accordingto one embodiment of the invention, or a copolymer of the polymerizablecompound according to one embodiment of the invention and an additionalcopolymerizable monomer.

Examples of the additional copolymerizable monomer include acommercially available product such as LC-242 (manufactured by BASF),the compounds disclosed in JP-A-2007-002208, JP-A-2009-173893,JP-A-2009-274984, JP-A-2010-030979, JP-A-2010-031223, JP-A-2011-006360,WO2012/141245, WO2012/147904, WO2012/169424, WO2012/176679, andWO2013/018526, and the like.

Further examples of the additional copolymerizable monomer include4′-methoxyphenyl 4-(2-methacryloyloxyethyloxy)benzoate, biphenyl4-(6-methacryloyloxyhexyloxy)benzoate, 4′-cyanobiphenyl4-(2-acryloyloxyethyloxy)benzoate, 4′-cyanobiphenyl4-(2-methacryloyloxyethyloxy)benzoate, 3′,4′-difluorophenyl4-(2-methacryloyloxyethyloxy)benzoate, naphthyl4-(2-methacryloyloxyethyloxy)benzoate, 4-acryloyloxy-4′-decylbiphenyl,4-acryloyloxy-4′-cyanobiphenyl,4-(2-acryloyloxyethyloxy)-4′-cyanobiphenyl,4-(2-methacryloyloxyethyloxy)-4′-methoxybiphenyl,4-(2-methacryloyloxyethyloxy)-4′-(4″-fluorobenzyloxy)-biphenyl,4-acryloyloxy-4′-propylcyclohexylphenyl,4-methacryloyl-4′-butylbicyclohexyl, 4-acryloyl-4′-amyltolane,4-acryloyl-4′-(3,4-difluorophenyl)bicyclohexyl, (4-amylphenyl)4-(2-acryloyloxyethyl)benzoate, (4-(4′-propylcyclohexyl)phenyl)4-(2-acryloyloxyethyl)benzoate, and the like.

A polyfunctional monomer that includes a plurality of polymerizableunsaturated groups (e.g., acryloyl group, methacryloyl group, vinylgroup, and allyl group) may also be used as the additionalcopolymerizable monomer.

Examples of such a polyfunctional monomer include an alkanedioldiacrylate such as 1,2-butanediol diacrylate, 1,3-butanediol diacrylate,1,4-butanediol diacrylate, neopentanediol diacrylate, and 1,6-hexanedioldiacrylate; an alkanediol dimethacrylate such as 1,2-butanedioldimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanedioldimethacrylate, neopentanediol dimethacrylate, and 1,6-hexanedioldimethacrylate; ethylene glycol diacrylate, and a polyethylene glycoldiacrylate such as diethylene glycol diacrylate, triethylene glycoldiacrylate, and tetraethylene glycol diacrylate; propylene glycoldiacrylate, and a polypropylene glycol diacrylate such as dipropyleneglycol diacrylate, tripropylene glycol diacrylate, and tetrapropyleneglycol diacrylate; ethylene glycol dimethacrylate, and a polyethyleneglycol dimethacrylate such as diethylene glycol dimethacrylate,triethylene glycol dimethacrylate, and tetraethylene glycoldimethacrylate; propylene glycol dimethacrylate, and a polypropyleneglycol dimethacrylate such as dipropylene glycol dimethacrylate,tripropylene glycol dimethacrylate, and tetrapropylene glycoldimethacrylate; ethylene glycol divinyl ether, and a polyethylene glycoldivinyl ether such as diethylene glycol divinyl ether, triethyleneglycol divinyl ether, and tetraethylene glycol divinyl ether; ethyleneglycol diallyl ether, and a polyethylene glycol diallyl ether such asdiethylene glycol diallyl ether, triethylene glycol diallyl ether, andtetraethylene glycol diallyl ether; bisphenol F ethoxylate diacrylate;bisphenol F ethoxylate dimethacrylate; bisphenol A ethoxylatediacrylate; bisphenol A ethoxylate dimethacrylate; trimethylolpropanetriacrylate; trimethylolpropane trimethacrylate; trimethylolpropaneethoxylate triacrylate; trimethylolpropane ethoxylate trimethacrylate;trimethylolpropane propoxylate triacrylate; trimethylolpropanepropoxylate trimethacrylate; isocyanuric acid ethoxylate triacrylate;glycerol ethoxylate triacrylate; glycerol propoxylate triacrylate;pentaerythritol ethoxylate tetraacrylate; ditrimethylolpropaneethoxylate tetraacrylate; dipentaerythritol ethoxylate hexacrylate; andthe like.

The polymerizable compound according to one embodiment of the inventionmay be (co)polymerized optionally together with the additionalcopolymerizable monomer in the presence of an appropriate initiator. Theinitiator may be used in a ratio similar to that of the initiatorincluded in the polymerizable composition.

When the polymer according to one embodiment of the invention is acopolymer of the polymerizable compound according to one embodiment ofthe invention and the additional copolymerizable monomer, the content ofstructural units derived from the polymerizable compound according toone embodiment of the invention is not particularly limited, but ispreferably 0.1 to 50 wt %, and more preferably 1 to 40 wt %, based onthe total structural units. When the content of structural units derivedfrom the polymerizable compound is within the above range, a polymerthat has a high glass transition temperature (Tg) and high hardness canbe obtained.

The polymer (1) may be produced by (A) (co)polymerizing thepolymerizable compound optionally together with the additionalcopolymerizable monomer in an appropriate organic solvent in thepresence of an appropriate initiator, isolating the target polymer,dissolving the polymer in an appropriate organic solvent to prepare asolution, applying the solution to an appropriate substrate to obtain afilm, and drying the film, followed by optional heating, or (B) applyinga solution prepared by dissolving the polymerizable compound and aninitiator in an organic solvent optionally together with the additionalcopolymerizable monomer to a substrate using a known coating method,removing the solvent, and effecting polymerization by applying heat oractivated energy rays, for example.

Examples of the initiator include those mentioned above in connectionwith the initiator that is included in the polymerizable composition.

The organic solvent used for polymerization when implementing the method(A) is not particularly limited as long as the organic solvent is inert.Examples of the organic solvent include an aromatic hydrocarbon such astoluene, xylene, and mesitylene; a ketone such as cyclohexanone,cyclopentanone, and methyl ethyl ketone; an acetate such as butylacetate and amyl acetate; a halogenated hydrocarbon such as chloroform,dichloromethane, and dichloroethane; an ether such as cyclopentyl methylether, tetrahydrofuran, and tetrahydropyran; and the like. It ispreferable to use a compound having a boiling point of 60 to 250° C.,and more preferably 60 to 150° C., from the viewpoint of handlingcapability.

Examples of the organic solvent used to dissolve the polymer whenimplementing the method (A), and the organic solvent used for the method(B), include a ketone-based solvent such as acetone, methyl ethylketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; anester-based solvent such as butyl acetate and amyl acetate; ahalogenated hydrocarbon-based solvent such as dichloromethane,chloroform, and dichloroethane; an ether-based solvent such astetrahydrofuran, tetrahydropyran, 1,2-dimethoxyethane, 1,4-dioxane,cyclopentyl methyl ether, and 1,3-dioxolane; an aprotic polar solventsuch as N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone, and N-methylpyrrolidone; and the like. Amongthese, a compound having a boiling point of 60 to 200° C. is preferablefrom the viewpoint of handling capability. These solvents may be usedeither alone or in combination.

A substrate formed of a known organic or inorganic material may be usedas the substrate. Examples of the organic material include apolycycloolefin (e.g., Zeonex and Zeonor (registered trademark,manufactured by Zeon Corporation); Arton (registered trademark,manufactured by JSR Corporation); and Apel (registered trademark,manufactured by Mitsui Chemicals Inc.)), polyethylene terephthalate, apolycarbonate, a polyimide, a polyamide, polymethyl methacrylate,polystyrene, polyvinyl chloride, polytetrafluoroethylene, cellulose,cellulose triacetate, polyethersulfone, and the like. Examples of theinorganic material include silicon, glass, calcite, and the like. It ispreferable to use a substrate formed of an organic material.

The substrate may be a single-layer substrate, or may be a laminate.

The substrate is preferably a substrate formed of an organic material,and more preferably a resin film that is formed of the organic material.

The polymer solution (method (A)) or the solution subjected topolymerization (method (B)) may be applied to the substrate using aknown coating method. Examples of the coating method include a curtaincoating method, an extrusion coating method, a roll coating method, aspin coating method, a dip coating method, a bar coating method, a spraycoating method, a slide coating method, a print coating method, and thelike.

(2) Polymer Obtained by Polymerizing Polymerizable Composition

The polymer according to one embodiment of the invention can be easilyobtained by polymerizing the polymerizable composition according to oneembodiment of the invention. It is preferable to use the polymerizablecomposition that includes the initiator (particularly a photoinitiator)in order to more efficiently effect polymerization.

Specifically, it is preferable to produce the polymer according to oneembodiment of the invention using the method (B) that applies thepolymerizable composition according to one embodiment of the inventionto a substrate, and polymerizes the applied polymerizable composition.Examples of the substrate include a substrate used to produce anoptically anisotropic product (described later), and the like.

The polymerizable composition according to one embodiment of theinvention may be applied to the substrate using a known coating method(e.g., bar coating method, spin coating method, roll coating method,gravure coating method, spray coating method, die coating method, capcoating method, or dipping method). A known organic solvent may be addedto the polymerizable composition according to one embodiment of theinvention in order to improve the applicability of the polymerizablecomposition. In this case, it is preferable to remove the organicsolvent by natural drying, drying by heating, drying under reducedpressure, drying by heating under reduced pressure, or the like, afterapplying the polymerizable composition to the substrate.

The polymerizable compound according to one embodiment of the inventionor the polymerizable composition according to one embodiment of theinvention may be polymerized by applying activated energy rays, orutilizing a thermal polymerization method, for example. It is preferableto polymerize the polymerizable compound or the polymerizablecomposition by applying activated energy rays since heating isunnecessary (i.e., the reaction can be effected at room temperature). Itis preferable to apply light (e.g., ultraviolet rays) to thepolymerizable compound or the polymerizable composition since theoperation is simple.

The temperature during application of light (irradiation) is preferablyset to 30° C. or less. The irradiance is normally set to 1 W/m² to 10kW/m², and preferably 5 W/m² to 2 kW/m².

A polymer obtained by polymerizing the polymerizable compound accordingto one embodiment of the invention or the polymerizable compositionaccording to one embodiment of the invention may be removed from thesubstrate, and used alone, or may be used directly as an organicmaterial of an optical film or the like without removing it from thesubstrate.

The number average molecular weight of the polymer according to oneembodiment of the invention thus obtained is preferably 500 to 500,000,and more preferably 5000 to 300,000. When the number average molecularweight of the polymer is within the above range, the resulting filmexhibits high hardness and an excellent handling capability. The numberaverage molecular weight of the polymer may be determined by gelpermeation chromatography (GPC) using monodisperse polystyrene as astandard (eluant: tetrahydrofuran).

It is considered that the polymer according to one embodiment of theinvention has a structure in which crosslinking points are uniformlypresent within the molecule. The polymer according to one embodiment ofthe invention exhibits a high crosslinking efficiency and excellenthardness.

The polymer according to one embodiment of the invention makes itpossible to inexpensively produce an optical film that achieves uniformconversion of polarized light over a wide wavelength band, and exhibitssatisfactory performance.

4) Optically Anisotropic Product

An optically anisotropic product according to one embodiment of theinvention includes (is produced using) the polymer according to oneembodiment of the invention.

The optically anisotropic product according to one embodiment of theinvention may be obtained by forming an alignment film on a substrate,and forming a polymer film on the alignment film using the polymeraccording to one embodiment of the invention.

The alignment film is formed on the surface of the substrate in order toachieve the in-plane alignment of an organic semiconductor compound in asingle direction.

The alignment film may be obtained by applying a solution (alignmentfilm composition) that includes a polymer (e.g., polyimide, polyvinylalcohol, polyester, polyallylate, polyamideimide, or polyetherimide) tothe substrate to form a film, drying the film, and subjecting the filmto a rubbing treatment in one direction, for example.

The thickness of the alignment film is preferably 0.001 to 5 μm, andmore preferably 0.001 to 1 μm.

The rubbing treatment may be performed on the alignment film or thesubstrate. The rubbing treatment may be implemented using an arbitrarymethod. For example, the alignment film may be rubbed in a givendirection using a roll around which a cloth or felt formed of syntheticfibers (e.g., nylon) or natural fibers (e.g., cotton) is wound. It ispreferable to wash (clean) the alignment film with isopropyl alcohol orthe like after completion of the rubbing treatment in order to remove afine powder (foreign substance) formed during the rubbing treatment, andclean the surface of the alignment film.

The alignment film may be provided with a function of achieving in-planealignment in a single direction by applying polarized ultraviolet raysto the surface of the alignment film.

A liquid crystal layer may be formed on the alignment film using thepolymer according to one embodiment of the invention by utilizing themethod described above in connection with the polymer according to oneembodiment of the invention.

Since the optically anisotropic product according to one embodiment ofthe invention is produced using the polymer according to one embodimentof the invention, the optically anisotropic product can be produced atlow cost, achieves uniform conversion of polarized light over a widewavelength band, and exhibits satisfactory performance.

The optically anisotropic product according to one embodiment of theinvention may be applied as a retardation film, an alignment film for aliquid crystal display device (liquid crystal display), a polarizer, aviewing angle-improving film, a color filter, a low-pass filter, anoptical polarization prism, an optical filter, and the like.

EXAMPLES

The invention is further described below by way of examples. Note thatthe invention is not limited to the following examples.

Example 1 Synthesis of Compound 1

Step 1: Synthesis of Intermediate A

A four-necked reactor equipped with a thermometer was charged with 8.01g (105 mmol) of 2-hydrazinoethanol and 30 ml of 2-propanol under anitrogen stream to prepare a solution. After the addition of 2.00 g(11.8 mmol) of 2-chlorobenzothiazole to the solution, the mixture wasrefluxed for 3 hours. After completion of the reaction, the reactionmixture was cooled to 25° C., and added to 300 ml of water, followed byextraction with 500 ml of ethyl acetate. The ethyl acetate layer wasdried over anhydrous sodium sulfate, and sodium sulfate was filteredoff. Ethyl acetate was evaporated from the filtrate under reducedpressure using a rotary evaporator to obtain a white solid. The whitesolid was recrystallized from ethyl acetate to obtain 0.9 g of anintermediate A (yield: 35.8%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 7.66 (dd, 1H, J=1.0 Hz, 8.0 Hz),7.34 (dd, 1H, J=1.0 Hz, 7.5 Hz), 7.20 (ddd, 1H, J=1.0 Hz, 7.5 Hz, 8.0Hz), 6.98 (ddd, 1H, J-1.0 Hz, 7.5 Hz, 7.5 Hz), 5.37 (s, 2H), 4.86 (t,1H, J=5.5 Hz), 3.78 (t, 2H, J=6.5 Hz), 3.72 (dt, 2H, J=5.5 Hz, 6.5 Hz)

Step 2: Synthesis of Intermediate B

A three-necked reactor equipped with a thermometer was charged with17.98 g (104.42 mmol) of trans-1,4-cyclohexanedicarboxylic acid and 180ml of tetrahydrofuran (THF) under a nitrogen stream. After the additionof 6.58 g (57.43 mmol) of methanesulfonyl chloride to the mixture, thereactor was immersed in a water bath to adjust the temperature of thereaction mixture to 20° C. 6.34 g (62.65 mmol) of triethylamine (TEA)was added dropwise to the reaction mixture over 10 minutes whilemaintaining the temperature of the reaction mixture at 20 to 30° C.After the dropwise addition, the mixture was stirred at 25° C. for 2hours.

After the addition of 0.64 g (5.22 mmol) of 4-(dimethylamino)pyridineand 13.80 g (52.21 mmol) of 4-(6-acryloyloxyhex-1-yloxy)phenol(manufactured by DKSH) to the reaction mixture, the reactor was immersedin a water bath to adjust the temperature of the reaction mixture to 15°C. 6.34 g (62.65 mmol) of TEA was added dropwise to the reaction mixtureover 10 minutes while maintaining the temperature of the reactionmixture at 20 to 30° C. After the dropwise addition, the mixture wasstirred at 25° C. for 2 hours. After completion of the reaction, 1,000ml of distilled water and 100 ml of a saturated sodium chloride solutionwere added to the reaction mixture, followed by extraction twice with400 ml of ethyl acetate. The organic layer was collected and dried overanhydrous sodium sulfate, and sodium sulfate was filtered off. Thesolvent was evaporated from the filtrate using a rotary evaporator, andthe residue was purified by silica gel column chromatography(THF:toluene=1:9 (volume ratio (hereinafter the same)) to obtain 14.11 gof an intermediate B as a white solid (yield: 65%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 12.12 (s, 1H), 6.99 (d, 2H, J=9.0Hz), 6.92 (d, 2H, J=9.0 Hz), 6.32 (dd, 1H, J=1.5 Hz, 17.5 Hz), 6.17 (dd,1H, J=10.0 Hz, 17.5 Hz), 5.93 (dd, 1H, J=1.5 Hz, 10.0 Hz), 4.11 (t, 2H,J=6.5 Hz), 3.94 (t, 2H, J=6.5 Hz), 2.48-2.56 (m, 1H), 2.18-2.26 (m, 1H),2.04-2.10 (m, 2H), 1.93-2.00 (m, 2H), 1.59-1.75 (m, 4H), 1.35-1.52 (m,8H)

Step 3: Synthesis of Intermediate C

A three-necked reactor equipped with a thermometer was charged with 4.00g (9.56 mmol) of the intermediate B synthesized in the step 2 and 60 mlof THF under a nitrogen stream to prepare a homogeneous solution. Afterthe addition of 1.12 g (9.78 mmol) of methanesulfonyl chloride to thesolution, the reactor was immersed in a water bath to adjust thetemperature of the reaction mixture to 20° C. 1.01 g (9.99 mmol) of TEAwas added dropwise to the reaction mixture over 5 minutes whilemaintaining the temperature of the reaction mixture at 20 to 30° C.After the dropwise addition, the mixture was stirred at 25° C. for 2hours. After the addition of 0.11 g (0.87 mmol) of4-(dimethylamino)pyridine and 0.60 g (4.35 mmol) of2,5-dihydroxybenzaldehyde to the reaction mixture, the reactor wasimmersed in a water bath to adjust the temperature of the reactionmixture to 15° C. 1.10 g (10.87 mmol) of TEA was added dropwise to thereaction mixture over 5 minutes while maintaining the temperature of thereaction mixture at 20 to 30° C. After the dropwise addition, themixture was stirred at 25° C. for 2 hours. After completion of thereaction, 400 ml of distilled water and 50 ml of a saturated sodiumchloride solution were added to the reaction mixture, followed byextraction twice with 750 ml of ethyl acetate. The organic layer wascollected and dried over anhydrous sodium sulfate, and sodium sulfatewas filtered off. The solvent was evaporated from the filtrate using arotary evaporator, and the residue was dissolved in 100 ml of THF. 500ml of methanol was added to the solution to precipitate crystals, whichwere filtered off. The crystals were washed with methanol, and driedunder vacuum to obtain 2.51 g of an intermediate C as a white solid(yield: 62%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 10.02 (s, 1H), 7.67 (d, 1H, J=3.0Hz), 7.55 (dd, 1H, J=3.0 Hz, 8.5 Hz), 7.38 (d, 1H, J=8.5 Hz), 6.99-7.04(m, 4H), 6.91-6.96 (m, 4H), 6.32 (dd, 2H, J=1.5 Hz, 17.5 Hz), 6.17 (dd,2H, J=10.0 Hz, 17.5 Hz), 5.93 (dd, 2H, J=1.5 Hz, 10.0 Hz), 4.11 (t, 4H,J=6.5 Hz), 3.95 (t, 4H, J=6.5 Hz), 2.56-2.81 (m, 4H), 2.10-2.26 (m, 8H),1.50-1.76 (m, 16H), 1.33-1.49 (m, 8H)

Step 4: Synthesis of Intermediate D

A three-necked reactor equipped with a thermometer was charged with0.760 g (3.64 mmol) of the intermediate A synthesized in the step 1,3.60 g (3.46 mmol) of the intermediate C synthesized in the step 3, 5 mlof ethanol, and 20 ml of THF under a nitrogen stream to prepare asolution. After the addition of 80.4 mg (0.36 mmol) of(±)-10-camphorsulfonic acid to the solution, the mixture was stirred at40° C. for 9 hours. After completion of the reaction, 30 ml of ethanolwas added to the mixture to precipitate a solid, which was filtered off.The solid was washed with ethanol, and dried using a vacuum dryer toobtain 3.80 g of an intermediate D as a white solid (yield: 97.2%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.95 (s, 1H), 7.743-7.73 (m, 1H),7.69 (dd, 1H, J=0.5 Hz, 7.5 Hz), 7.65 (d, 1H, J=7.5 Hz), 7.35 (ddd, 1H,J=1.0 Hz, 7.0 Hz, 7.5 Hz), 7.19 (ddd, 1H, J=1.0 Hz, 7.5 Hz, 7.5 Hz),7.119-7.116 (m, 2H), 7.00-6.96 (m, 4H), 6.89-6.87 (m, 4H), 6.40 (dd, 2H,J=1.5 Hz, 17.5 Hz), 6.12 (dd, 2H, J=10.5 Hz, 17.5 Hz), 5.83 (dd, 2H,J=1.5 Hz, 10.5 Hz), 4.45 (t, 2H, J=5.5 Hz), 4.18 (t, 4H, J=8.0 Hz),4.07-4.02 (m, 2H), 3.946 (t, 2H, J=6.5 Hz), 3.943 (t, 2H, J=6.5 Hz),2.85-2.80 (br, 1H), 2.73-2.55 (m, 4H), 2.37-2.27 (m, 8H), 1.83-1.65 (m,16H), 1.55-1.42 (m, 8H)

Step 5: Synthesis of Compound 1

A three-necked reactor equipped with a thermometer was charged with 2.00g (1.78 mmol) of the intermediate D synthesized in the step 4 and 20 mlof THF under a nitrogen stream to prepare a solution. The solution wascooled to 0° C. After the addition of 240 mg (2.66 mmol) of acryloylchloride and 358 mg (3.54 mmol) of TEA to the solution, the mixture wasstirred at 25° C. for 5 hours. After completion of the reaction, thereaction mixture was added to 50 ml of water, followed by extractionwith 200 ml of ethyl acetate. The ethyl acetate layer was dried overanhydrous sodium sulfate, and sodium sulfate was filtered off. Ethylacetate was evaporated from the filtrate under reduced pressure using arotary evaporator to obtain a white solid. The white solid was purifiedby silica gel column chromatography (chloroform:ethyl acetate=95:5) toobtain 1.16 g of a compound 1 as a white solid (yield: 55.2%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 8.02 (s, 1H), 7.766-7.760 (m, 1H),7.70 (dd, 1H, J=0.5 Hz, 8.0 Hz), 7.68 (d, 1H, J=8.0 Hz), 7.36 (ddd, 1H,J=1.0 Hz, 7.5 Hz, 8.0 Hz), 7.19 (ddd, 1H, J=1.0 Hz, 7.5 Hz, 8.0 Hz),7.12 (d, 2H, J=1.5 Hz), 7.00-6.96 (m, 4H), 6.89-6.87 (m, 4H), 6.41 (dd,1H, J=1.5 Hz, 17.5 Hz), 6.40 (dd, 2H, J=1.5 Hz, 17.5 Hz), 6.13 (dd, 2H,J=10.5 Hz, 17.5 Hz), 6.10 (dd, 1H, J=10.5 Hz, 17.5 Hz), 5.85 (dd, 1H,J=1.5 Hz, 10.5 Hz), 5.82 (dd, 2H, J=1.5 Hz, 10.5 Hz), 4.59 (t, 2H, J=6.5Hz), 4.49 (t, 2H, J=6.5 Hz), 4.18 (t, 4H, J=6.5 Hz), 3.95 (t, 4H, J=6.5Hz), 2.88-2.79 (m, 1H), 2.70-2.56 (m, 3H), 2.38-2.26 (m, 8H), 1.85-1.64(m, 16H), 1.56-1.42 (m, 8H)

Example 2 Synthesis of Compound 2

Step 1: Synthesis of Intermediate E

A four-necked reactor equipped with a thermometer was charged with 20 g(144.8 mmol) of 2,5-dihydroxybenzaldehyde, 105.8 g (362.0 mmol) of4-(6-acryloylhex-1-yloxy)benzoic acid (manufactured by DKSH Japan K.K.),5.3 g (43.4 mmol) of 4-(dimethylamino)pyridine, and 200 ml ofN-methylpyrrolidone under a nitrogen stream to prepare a homogeneoussolution. After the addition of 83.3 g (434.4 mol) of1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (WSC) to thesolution, the mixture was stirred at 25° C. for 12 hours. Aftercompletion of the reaction, the reaction mixture was added to 1.5 l ofwater, followed by extraction with 500 ml of ethyl acetate. The ethylacetate layer was dried over anhydrous sodium sulfate, and sodiumsulfate was filtered off. Ethyl acetate was evaporated from the filtrateunder reduced pressure using a rotary evaporator to obtain a lightyellow solid. The light yellow solid was purified by silica gel columnchromatography (toluene:ethyl acetate=9:1) to obtain 75 g of anintermediate E as a white solid (yield: 75.4%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (400 MHz, CDCl₃, TMS, δ ppm): 10.20 (s, 1H), 8.18-8.12 (m, 4H),7.78 (d, 1H, J=2.8 Hz), 7.52 (dd, 1H, J=2.8 Hz, 8.7 Hz), 7.38 (d, 1H,J=8.7 Hz), 7.00-6.96 (m, 4H), 6.40 (dd, 2H, J=1.4 Hz, 17.4 Hz), 6.12(dd, 2H, J=10.6 Hz, 17.4 Hz), 5.82 (dd, 2H, J=1.4 Hz, 10.6 Hz), 4.18 (t,4H, J=6.4 Hz), 4.08-4.04 (m, 4H), 1.88-1.81 (m, 4H), 1.76-1.69 (m, 4H),1.58-1.42 (m, 8H)

Step 2: Synthesis of Intermediate F

A three-necked reactor equipped with a thermometer was charged with0.385 g (1.84 mmol) of the intermediate A synthesized in the step 1 ofExample 1, 1.20 g (1.75 mmol) of the intermediate E synthesized in thestep 2, 3 ml of ethanol, and 15 ml of THF under a nitrogen stream toprepare a solution. After the addition of 40.7 mg (0.17 mmol) of(±)-10-camphorsulfonic acid to the solution, the mixture was stirred at40° C. for 8 hours. After completion of the reaction, 20 ml of ethanolwas added to the mixture to precipitate a solid, which was filtered off.The solid was washed with ethanol, and dried using a vacuum dryer toobtain 1.22 g of an intermediate F as a white solid (yield: 79.2%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 8.20 (d, 2H, J=9.0 Hz), 8.18 (d,2H, J=9.0 Hz), 8.01 (s, 1H), 7.89 (d, 1H, J=2.5 Hz), 7.62 (d, 1H, J=8.0Hz), 7.61 (d, 1H, J=8.0 Hz), 7.33-7.28 (m, 3H), 7.15 (ddd, 1H, J=1.0 Hz,7.5 Hz, 7.5 Hz), 7.09 (d, 4H, J=9.0 Hz), 6.41 (dd, 2H, J=1.5 Hz, 17.5z), 6.14 (dd, 2H, J=10.5 Hz, 17.5 Hz), 5.84 (dd, 2H, J=1.5 Hz, 10.5 Hz),4.36 (t, 2H, J=5.5 Hz), 4.194 (t, 2H, J=6.5 Hz), 4.192 (t, 2H, J=6.5Hz), 4.08 (t, 2H, J=6.5 Hz), 4.07 (t, 2H, J=6.5 Hz), 3.90 (t, 2H, J=5.5Hz), 3.15 (br, 1H), 1.90-1.84 (m, 4H), 1.77-1.66 (m, 4H), 1.59-1.45 (m,8H)

Step 3: Synthesis of Compound 2

A three-necked reactor equipped with a thermometer was charged with 1.20g (1.37 mmol) of the intermediate F synthesized in the step 2 and 15 mlof THF under a nitrogen stream to prepare a solution. The solution wascooled to 0° C. After the addition of 247 mg (2.73 mmol) of acryloylchloride and 416 mg (4.11 mmol) of TEA to the solution, the mixture wasstirred at 25° C. for 2 hours. After completion of the reaction, thereaction mixture was added to 50 ml of water, followed by extractionwith 200 ml of ethyl acetate. The ethyl acetate layer was dried overanhydrous sodium sulfate, and sodium sulfate was filtered off. Ethylacetate was evaporated from the filtrate under reduced pressure using arotary evaporator to obtain a white solid. The white solid was purifiedby silica gel column chromatography (chloroform:methanol=97:3) to obtain1.02 g of a compound 2 as a white solid (yield: 79.9%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 8.21 (d, 2H, J=8.5 Hz), 8.19 (d,2H, J=8.5 Hz), 8.07 (s, 1H), 7.920-7.915 (m, 1H), 7.64-7.62 (m, 2H),7.32 (ddd, 1H, J=1.5 Hz, 7.5 Hz, 7.5 Hz), 7.29-7.28 (m, 2H), 7.14 (ddd,1H, J=1.5 Hz, 7.5 Hz, 7.5 Hz), 7.01 (d, 2H, J=8.5 Hz), 6.99 (d, 2H,J=8.5 Hz), 6.42 (dd, 2H, J=1.5 Hz, 17.5 Hz), 6.21 (dd, 1H, J=1.5 Hz,17.5 Hz), 6.14 (dd, 2H, J=10.5 Hz, 17.5 Hz), 5.94 (dd, 1H, J=10.5 Hz,17.5 Hz), 5.83 (dd, 2H, J=1.5 Hz, 10.5 Hz), 5.73 (dd, 1H, J=1.5 Hz, 10.5Hz), 4.54 (t, 2H, 6.5 Hz), 4.43 (t, 2H, 6.5 Hz), 4.20 (t, 4H, J=6.5 Hz),4.08 (t, 2H, J=6.5 Hz), 4.07 (t, 2H, J=6.5 Hz), 1.89-1.83 (m, 4H),1.77-1.72 (m, 4H), 1.59-1.45 (m, 8H)

Comparative Example 1 Synthesis of Compound 1r

Step 1: Synthesis of Intermediate α

A three-necked reactor equipped with a thermometer was charged with 3.00g (17.69 mmol) of 2-chlorobenzothiazole, 7.65 g (70.74 mmol) ofphenylhydrazine, and 30 ml of ethylene glycol under a nitrogen stream toprepare a solution. The solution was heated to 140° C., and reacted for5 hours. 300 ml of distilled water was added to the reaction mixture,followed by extraction twice with 100 ml of ethyl acetate. The ethylacetate layer was dried over anhydrous sodium sulfate, and sodiumsulfate was filtered off. After concentrating the filtrate using arotary evaporator, 15 ml of THF was added to the concentrate to preparea solution. The solution was added to 300 ml of distilled water toprecipitate a solid, which was washed with distilled water, and driedunder vacuum to obtain a yellow solid. A flask was charged with theyellow solid. After the addition of 50 ml of toluene, the mixture wasstirred for 30 minutes, and filtered to remove a toluene-insoluble solidcomponent. The filtrate was concentrated using a rotary evaporator, andthe concentrate was purified by silica gel column chromatography(THF:toluene=2:50) to obtain 0.94 g of an intermediate a as a yellow oil(yield: 22%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 8.01 (dd, 2H, J=1.0 Hz, 9.0 Hz),7.78 (dd, 1H, J=1.0 Hz, 8.0 Hz), 7.51 (dd, 1H, J=1.0 Hz, 8.0 Hz), 7.43(dd, 2H, J=7.5 Hz, 8.5 Hz), 7.28 (dt, 1H, J=1.0 Hz, 7.5 Hz), 7.08-7.16(m, 2H), 6.26 (s, 2H)

Step 2: Synthesis of Compound 1r

A three-necked reactor equipped with a thermometer was charged with 1.00g (1.06 mmol) of the intermediate C synthesized in the step 3 of Example1 and 30 ml of THF under a nitrogen stream to prepare a solution. Afterthe addition of 0.22 ml (0.22 mmol) of 1 N hydrochloric acid and 0.38 g(1.60 mmol) of the intermediate α synthesized in the step 1 to thesolution, the mixture was reacted at 40° C. for 2 hours. The reactionmixture was concentrated using a rotary evaporator, and the concentratewas purified by silica gel column chromatography (chloroform:THF=40:1)to obtain 1.14 g of a compound 1r as a light yellow solid (yield: 95%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.82 (d, 1H, J=2.5 Hz), 7.73 (dd,1H, J=1.0 Hz, 8.0 Hz), 7.64-7.70 (m, 2H), 7.60 (d, 2H, J=7.5 Hz),7.35-7.42 (m, 3H), 7.30 (dt, 1H, J=1.0 Hz, 7.5 Hz), 7.18 (dt, 1H, J=1.0Hz, 7.5 Hz), 7.03-7.12 (m, 2H), 7.00 (d, 2H, J=9.0 Hz), 6.99 (d, 2H,J=9.0 Hz), 6.90 (d, 2H, J=9.0 Hz), 6.89 (d, 2H, J=9.0 Hz), 6.41 (dd, 1H,J=1.5 Hz, 17.5 Hz), 6.41 (dd, 1H, J=1.5 Hz, 17.5 Hz), 6.13 (dd, 1H,J=10.5 Hz, 17.5 Hz), 6.13 (dd, 1H, J=10.5 Hz, 17.5 Hz), 5.82 (dd, 1H,J=1.5 Hz, 10.5 Hz), 5.82 (dd, 1H, J=1.5 Hz, 10.5 Hz), 4.18 (t, 2H, J=6.5Hz), 4.18 (t, 2H, J=6.5 Hz), 3.92-3.98 (m, 4H), 2.56-2.71 (m, 2H),2.41-2.50 (m, 1H), 2.27-2.40 (m, 5H), 2.12-2.22 (m, 2H), 1.64-1.91 (m,14H), 1.41-1.56 (m, 10H), 1.19-1.31 (m, 2H)

The phase transition temperature was measured as described below usingthe compounds 1 and 2 respectively obtained in Examples 1 and 2, thecompound 1r obtained in Comparative Example 1, and the compound 2r(“LC242” manufactured by BASF) of Reference Example 1 that was used inComparative Example 3.

Measurement of Phase Transition Temperature

10 mg of each compound (compounds 1, 2, 1r, and 2r) was weighed, andplaced in a solid state between two glass substrates provided with apolyimide alignment film subjected to a rubbing treatment (manufacturedby E.H.C. Co., Ltd.). The substrates were placed on a hot plate, heatedfrom 40° C. to 250° C., and cooled to 40° C. A change in structureduring a change in temperature was observed using a polarizingmicroscope (“ECLIPSE LV100 POL” manufactured by Nikon Corporation).

The phase transition temperature measurement results are shown inTable 1. In Table 1, “C” refers to “crystal”, “N” refers to “nematic”,and “I” refers to “isotropic”. The term “crystal” means that the testcompound was in a solid phase, the term “nematic” means that the testcompound was in a nematic liquid crystal phase, and the term “isotropic”means that the test compound was in an isotropic liquid phase.

TABLE 1 Example Compound Phase transition temperature Example 1 Compound1

Example 2 Compound 2

Comparative Example 1 Compound 1r

Reference Example 1 Compound 2r

Example 3

1.0 g of the compound 1 obtained in Example 1, 30 mg of a photoinitiator(“Irgacure 379EG” manufactured by BASF), and 100 mg of a 1%cyclopentanone solution of a surfactant (“KH-40” manufactured by AGCSeimi Chemical Co., Ltd.) were dissolved in 2.3 g of cyclopentanone. Thesolution was filtered through a disposable filter having a pore size of0.45 μm to prepare a polymerizable composition 1.

Example 4

A polymerizable composition 2 was prepared in the same manner as inExample 3, except that the compound 2 obtained in Example 2 was usedinstead of the compound 1.

Comparative Example 2

A polymerizable composition 1r was prepared in the same manner as inExample 3, except that the compound 1r obtained in Comparative Example 1was used instead of the compound 1.

Comparative Example 3

A polymerizable composition 2r was prepared in the same manner as inExample 3, except that the compound 2r was used instead of the compound1.

Measurement of Retardation and Evaluation 1 of Wavelength Dispersion (i)Formation of Liquid Crystal Layer Using Polymerizable Composition

Each polymerizable composition (polymerizable compositions 1 to 4) wasapplied to a transparent glass substrate (provided with a polyimidealignment film subjected to a rubbing treatment) (manufactured by E.H.C.Co., Ltd.) using a #4 wire bar. The resulting film was dried for 1minute at the temperature shown in Table 2, and subjected to analignment treatment for 1 minute at the temperature shown in Table 2 toform a liquid crystal layer. Ultraviolet rays were applied (directly) tothe liquid crystal layer at a dose of 2,000 mJ/cm² or 2,500 mJ/cm² toeffect polymerization to prepare a wavelength dispersion measurementsample.

(ii) Measurement of Retardation

The retardation of the sample between 400 nm and 800 nm was measuredusing an ellipsometer (“M2000U” manufactured by J. A. Woollam).

(iii) Evaluation of Wavelength Dispersion

The wavelength dispersion was evaluated based on the values α and β thatwere calculated as described below using the measured retardation.

α=(retardation at 449.9 nm)/(retardation at 548.5 nm)

β=(retardation at 650.2 nm)/(retardation at 548.5 nm)

Table 2 shows the thickness (μm) of each liquid crystal polymer filmobtained by polymerizing the polymerizable composition, the retardation(Re) at a wavelength of 548.5 nm, and the values α and β.

Note that the value α is smaller than 1, and the value β is larger than1 when an ideal wideband wavelength dispersion (reverse wavelengthdispersion) is achieved. The values α and β are almost identical to eachother when flat wavelength dispersion is achieved. The value α is largerthan 1, and the value β is smaller than 1 when normal dispersion isachieved. A flat wavelength dispersion that ensures that the values αand β are almost identical to each other, and a reverse wavelengthdispersion that ensures that the value α is smaller than 1, and thevalue β is larger than 1, are preferable, and the reverse wavelengthdispersion that ensures that the value α is smaller than 1, and thevalue β is larger than 1, is particularly preferable.

TABLE 2 Drying Alignment treatment Polymerizable Polymerizabletemperature temperature Dose compound composition (° C.) (° C.) (mJ)Example 3 1  1  120 23 2,000 2,500 Example 4 2  2  100 24 2,000 2,500Comparative 1r 1r 120 25 2,000 Example 2 2,500 Comparative 2r 2r  80 262,000 Example 3 2,500 Change in Thickness Re Wavelength wavelength (μm)(548.5 nm) α β dispersion dispersion Example 3 1.572 134.69 0.906 1.033Reverse wavelength Did not occur dispersion 1.571 134.55 0.906 1.033Reverse wavelength dispersion Example 4 1.470 145.26 0.986 0.987 Flatwavelength Did not occur dispersion 1.475 145.33 0.986 0.987 Flatwavelength dispersion Comparative 1.900 148.13 0.879 1.024 Reversewavelength Occurred Example 2 dispersion 1.500 123.80 0.976 0.989 Flatwavelength dispersion Comparative 1.479 222.90 1.086 0.970 Normalwavelength Did not occur Example 3 dispersion 1.481 223.10 1.087 0.970Normal wavelength dispersion

The optically anisotropic products of Examples 3 and 4 obtainedcompounds 1 and 2 showed an ideal reverse wavelength dispersion, and didnot show a change in wavelength dispersion depending on the dose ofultraviolet rays.

The optically anisotropic product of Comparative Example 2 obtainedusing the compound 1r showed reverse wavelength dispersion when thepolymerizable composition was polymerized by applying ultraviolet raysat a dose of 2,000 mJ/cm², but showed flat wavelength dispersion whenthe polymerizable composition was polymerized by applying ultravioletrays at a dose of 2,500 mJ/cm². Specifically, the optically anisotropicproduct of Comparative Example 2 showed a change in wavelengthdispersion depending on the dose of ultraviolet rays.

The optically anisotropic product of Comparative Example 3 obtainedusing the compound 2r did not show a change in wavelength dispersiondepending on the dose of ultraviolet rays, but showed normal wavelengthdispersion.

The embodiments of the invention thus provide a polymerizable compound,a polymerizable composition, and a polymer that have a practical lowmelting point, exhibit excellent solubility in a general-purposesolvent, can be produced at low cost, and can produce an optical filmthat achieves uniform conversion of polarized light over a widewavelength band, and does not show a change in wavelength dispersioneven when the dose of ultraviolet rays applied to effect curing isincreased, as well as an optically anisotropic product.

1. A polymerizable compound represented by a formula (I),

wherein each of Y¹ to Y⁹ independently represents a chemical singlebond, —O—, —S—, —O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, —NR¹—C(═O)—,—C(═O)—NR¹—, —O—C(═O)—NR¹—, —NR¹—C(═O)—O—, —NR¹—C(═O)—NR¹—, —O—NR¹—, or—NR¹—O—, R¹ represents a hydrogen atom or an alkyl group having 1 to 6carbon atoms, each of G¹ and G² independently represents a substitutedor unsubstituted divalent linear aliphatic group having 1 to 20 carbonatoms, each of Z¹, Z², and Z³ independently represents an alkenyl grouphaving 2 to 10 carbon atoms that is substituted with a halogen atom, orunsubstituted, A^(x) represents a group represented by a formula (II),

wherein X represents —NR²—, an oxygen atom, a sulfur atom, —SO—, or—SO₂—, and R² represents a hydrogen atom or an alkyl group having 1 to 6carbon atoms, provided that an arbitrary C—H is optionally substitutedwith a nitrogen atom, D represents a substituted or unsubstitutedalkylene group having 1 to 20 carbon atoms that optionally includes —O—,—S—, —O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, —NR³—C(═O)—, —C(═O)—NR³—, —NR³—,or —C(═O)—, or a substituted or unsubstituted cycloalkanediyl grouphaving 3 to 20 carbon atoms, provided that a case where the alkylenegroup includes two or more contiguous —O— or —S— is excluded, and R³represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,A¹ represents a substituted or unsubstituted trivalent aromatic group,each of A² and A³ independently represents a substituted orunsubstituted divalent alicyclic hydrocarbon group having 3 to 30 carbonatoms, each of A⁴ and A⁵ independently represents a substituted orunsubstituted divalent aromatic group having 4 to 30 carbon atoms, Q¹represents a hydrogen atom, or a substituted or unsubstituted alkylgroup having 1 to 6 carbon atoms, and m and n are independently 0 or 1.2. The polymerizable compound according to claim 1, wherein D is asubstituted or unsubstituted alkylene group having 1 to 20 carbon atomsthat optionally includes —O—, —S—, —O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, or—C(═O)—, provided that a case where the alkylene group includes two ormore contiguous —O— or —S— is excluded.
 3. The polymerizable compoundaccording to claim 1, wherein A¹ is a substituted or unsubstitutedtrivalent benzene ring group, or a substituted or unsubstitutedtrivalent naphthalene ring group.
 4. The polymerizable compoundaccording to claim 1, wherein each of Y¹ to Y⁹ is independently achemical single bond, —O—, —O—C(═O)—, —C(═O)—O—, or —O—C(═O)—O—.
 5. Thepolymerizable compound according to claim 1, wherein each of Z¹, Z², andZ³ is independently CH₂═CH—, CH₂═C(CH₃)—, or CH₂═C(Cl)—.
 6. Thepolymerizable compound according to claim 1, wherein each of G¹ and G²is independently a substituted or unsubstituted divalent aliphatic grouphaving 1 to 12 carbon atoms that optionally includes —O—, —O—C(═O)—,—C(═O)—O—, or —C(═O)—, provided that a case where the aliphatic groupincludes two or more contiguous —O— is excluded.
 7. The polymerizablecompound according to claim 1, wherein each of G¹ and G² isindependently an alkylene group having 1 to 12 carbon atoms.
 8. Apolymerizable composition comprising at least one type of thepolymerizable compound according to claim
 1. 9. A polymerizablecomposition comprising at least one type of the polymerizable compoundaccording to claim 1, and an initiator.
 10. A polymer obtained bypolymerizing the polymerizable compound according to claim
 1. 11. Thepolymer according to claim 10, the polymer being a liquid crystalpolymer.
 12. An optically anisotropic product comprising the polymeraccording to claim
 11. 13. A polymer obtained by polymerizing thepolymerizable composition according to claim
 8. 14. A polymer obtainedby polymerizing the polymerizable composition according to claim
 9. 15.The polymer according to claim 13, the polymer being a liquid crystalpolymer.
 16. An optically anisotropic product comprising the polymeraccording to claim
 15. 17. A polymerizable compound represented byformula (1) or (2).


18. An antireflective film comprising the optically anisotropic productaccording to claim 12 and a polarizer.
 19. An optical film comprisingthe polymer according to claim 10.